Oxidant dopant agent for conductive polymer production, and a solution thereof, and a conductive polymer prepared by using either of them, as well as an electrolyte capacitor using the conductive polymer as an electrolyte

ABSTRACT

There is provided an oxidant dopant agent for conductive polymer production, and a solution thereof, in which they are capable of producing a conductive polymer suitable in producing an electrolyte capacitor having a low leak current. There is also provided a conductive polymer prepared by using either of them. There is also provided an electrolyte capacitor having a low leak current. The oxidant dopant agent includes: an organic ferric sulfonate; and at least one kind selected from the group consisting of phosphoric acid, phosphate, phosphorous acid, phosphite, boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoric acid and dithiophosphate. The solution includes the oxidant dopant agent dissolved in water, an alcohol or a mixture of water and an alcohol. A conductive polymer is prepared by means of oxidation polymerization of a monomer such as thiophene or its derivative. The conductive polymer is used as an electrolyte to provide an electrolyte capacitor.

An oxidant dopant agent for conductive polymer production, and asolution thereof, and

a conductive polymer prepared by using either of them, as well as

an electrolyte capacitor using the conductive polymer as an electrolyte

TECHNICAL FIELD

The present invention relates to an oxidant dopant agent for conductivepolymer production, and a solution thereof. The present invention alsorelates to a conductive polymer prepared by using either of them, aswell as an electrolyte capacitor using the conductive polymer as anelectrolyte.

BACKGROUND OF THE INVENTION

Having a high conductivity, conductive polymers have been used as anelectrolyte in aluminum electrolyte capacitors, tantalum electrolytecapacitors, niobium electrolyte capacitors, and etc.

The conductive polymers used in such an application can be obtained bymeans of chemical oxidation polymerization or electrolytic oxidationpolymerization of, for example, thiophene or its derivatives.

As a dopant, an organic sulfonic acid can be mainly used to carry out achemical oxidation polymerization of thiophene or its derivative asmentioned above. As an oxidant, a transition metal can be used. Inparticular, it is said that a ferric compound is suitable. Usually, aferric salt of an organic sulfonic acid can be used to serve as anoxidant dopant agent in carrying out the chemical oxidationpolymerization of thiophene or its derivative. (Patent Reference No. 1and Patent Reference No. 2.)

However, in case of using ferric salts of organic sulfonic acids as anoxidant dopant agent to prepare a conductive polymer, thereby obtainedelectrolyte capacitors using it have been involved in large amounts ofleak current. In particular, such problem of large amounts of leakcurrent could become significant especially in a condition of a hightemperature.

PRIOR ART REFERENCES Patent References

-   Patent Reference No. 1: Japanese Laid Open Patent Publication No.    2003-160647;-   Patent Reference No. 2: Japanese Laid Open Patent Publication No.    2004-265927

SUMMARY OF THE INVENTION The Objectives To Solve By The Invention

Therefore, the present invention relates to an oxidant dopant agent forconductive polymer production, and a solution thereof. They are capableof producing a conductive polymer suitable for producing an electrolytecapacitor having a low leak current. In addition, the present inventionrelates to a conductive polymer prepared by using either of the oxidantdopant agent or the solution thereof, in which the conductive polymer issuitable for producing an electrolyte capacitor having a low leakcurrent. Also, the present invention relates to an electrolyte capacitorusing the conductive polymer as an electrolyte, in which the electrolytecapacitor has a low leak current.

Means To Solve The Problem

As a result of zealous study to solve the problems as discussed above,the present invention has been accomplished based on the finding thatthe problems above can be solved by using an oxidant dopant agentprepared from an organic ferric sulfonate and a special additive such asa phosphoric acid type additive, a phosphorous acid type additive, aboric acid type additive, a thiophosphoric acid type additive or adithiophosphoric acid type additive.

That is, the present invention relates to an oxidant dopant agent forpreparing a conductive polymer, comprising: an organic ferric sulfonate;and at least one kind selected from the group consisting of phosphoricacid, phosphate, phosphorous acid, phosphite, boric acid, borate,thiophosphoric acid, thiophosphate, dithiophosphoric acid anddithiophosphate.

In addition, when adding a glycidyl group containing compound itsring-opening compound into the oxidant dopant agent for conductivepolymer preparation as mentioned above, an electrolyte capacitor can beprepared while giving it not only a characteristic of a low leakcurrent, but a characteristic, of a high breakdown voltage (i.e., it isalso excellent in the withstanding voltage property). Therefore, thescope of the present invention includes the oxidant dopant agent forconductive polymer preparation as identified above. The scope of thepresent invention also encompasses an oxidant dopant agent for preparingas conductive polymer which further includes a glycidyl group containingcompound or its ring-opening compound. Furthermore, the scope of thepresent invention can encompass a solution of the oxidant dopant agentfor conductive polymer preparation solution in which the oxidant dopantagent for conductive polymer preparation is dissolved in water, analcohol or a mixture with water and the alcohol. The scope of thepresent invention can also encompass a conductive polymer prepared bymeans of oxidation polymerization of a monomer such as thiophene or itsderivative by using the oxidant dopant agent for conductive polymerpreparation, or the solution thereof. The scope of the present inventioncan also encompass an electrolyte, capacitor using the conductivepolymer as an electrolyte.

Effects of the Invention

According to the present invention, there can be provided an oxidantdopant agent for conductive polymer preparation, and a solution thereof.These are capable of producing a conductive polymer suitable forproducing; an electrolyte capacitor having a low leak current.

Also, according to the present invention, by using the oxidant dopant,agent for conductive polymer preparation, or the solution thereof, therecan be provided a conductive polymer which is suitable for producing anelectrolyte capacitor having as low leak current.

In addition, by using the conductive polymer, there can be provided anelectrolyte capacitor having a low leak current.

EMBODIMENTS TO CARRY OUT THE INVENTION

As explained before, the oxidant dopant agent for conductive polymerpreparation of the present invention can be constituted by including anorganic ferric sulfonate; and at least one kind selected from the groupconsisting of phosphoric acid, phosphate, phosphorous acid, phosphite,boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoricacid and dithiophosphate. Here, the organic ferric sulfonate canincludes compounds which have been used in this field, and a largenumber of compounds are available for use. Therefore, its partner, thatis, the specific acid or an acid ester component, will be explainedfirst.

The acid or an acid ester component can include at least one kindselected from the group consisting of phosphoric acid, phosphate,phosphorous acid, phosphite, boric acid, borate, thiophosphoric acid,thiophosphate, dithiophosphoric acid and dithiophosphate. The phosphateabove can include methyl phosphate, dimethyl phosphate, trimethylphosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate,propyl phosphate, dipropyl phosphate, tripropyl phosphate, butylphosphate, dibutyl phosphate, tributyl phosphate, ethylhexyl phosphate,diethylhexyl phosphate, triethylhexyl phosphate, benzyl phosphate,dibenzyl phosphate, tribenzyl phosphate, phenyl phosphate, diphenylphosphate, triphenyl phosphate, trisethoxydiglycol phosphate,polyperfluoroethoxymethoxydifluoroethylpolyethyleneglycol phosphate,dimethyl-2-(glycidyloxy)ethyl phosphate, hexyl phosphate, dihexylphosphate, trihexyl phosphate, octyl phosphate, dioctyl phosphate,trioctyl phosphate, decyl phosphate, didecyl phosphate, tridecylphosphate, dodecyl phosphate, didodecyl phosphate, tridodecyl phosphate,acrylic phosphate, diacrylic phosphate, triacrylic phosphate, methacrylphosphate, dimethacryl phosphate, trimethacryl phosphate, phosphorusacid hydroxyethyl methacrylate, phosphorus acid dihydroxyethylmethacrylate, and phosphorus acid trihydroxyethyl methacrylate. Amongthe phosphates above, particularly favorable are a dialkyl phosphatesuch as dimethyl phosphate, diethyl phosphate, dipropyl phosphate,dibutyl phosphate; a diester phosphate such as dibenzyl phosphate anddiphenyl phosphate: and a triester phosphate such as tributyl phosphate,

The phosphite above can include methyl phosphite, dimethyl phosphite,trimethyl phosphite, ethyl phosphite, diethylphosphite, triethylphosphite, propyl phosphite, dipropyl phosphite, tripropyl phosphite,butyl phosphite, dibutyl phosphite, tributyl phosphite, ethylhexylphosphite, diethylhexyl phosphite, triethylhexyl phosphite, benzylphosphite, dibenzyl phosphite, tribenzyl phosphite, phenyl phosphite,diphenyl phosphite, triphenyl phosphite, trisethoxydiglycol phosphite,dimethyl-2-(glycidyloxy)ethyl phosphite, hexyl phosphite, dihexylphosphite, trihexyl phosphite, octyl phosphite, dioctyl phosphite,trioctyl phosphite, decyl phosphite, didecyl phosphite, tridecylphosphite, dodecyl phosphite, didodecyl phosphite, tridodecyl phosphite,acrylic phosphite, diacrylic phosphite, triacrylic phosphite, methacrylphosphite, dimethacryl phosphite, trimethacryl phosphite phosphorousacid hydroxyethyl methacrylate, phosphorous acid dihydroxyethylmethacrylate, and phosphorous acid trihydroxyethyl methacrylate. Amongthe phosphites above, particularly preferable are, for example, adialkyl phosphite such as dimethyl phosphite, diethyl phosphite,dipropyl phosphite, dibutyl phosphite, and diethylhexyl phosphite; adiester phosphite such as dibenzyl phosphite and diphenyl phosphite; anda triester phosphite such as tributyl phosphite.

The borate as mentioned above can include, for example, methyl borate,dimethyl borate, trimethyl borate, ethyl borate, diethyl borate,triethyl borate, propyl borate, dipropyl borate, tripropyl borate, butylborate, dibutyl borate, tributyl borate, ethylhexyl borate, diethylhexylborate, triethylhexyl borate, benzyl borate, dibenzyl borate, tribenzylborate, phenyl borate, diphenyl borate, triphenyl borate, hexyl borate,dihexyl borate, trihexyl borate, octyl borate, dioctyl borate, trioctylborate, decyl borate, didecyl borate, tridecyl borate, dodecyl borate,didodecyl borate, tridodecyl borate, acrylic borate, diacrylic borate,triacrylic borate, methacryl borate, dimethacryl borate, andtrimethacryl borate. Among the borates above, particularly preferableare a dialkyl borate such as dimethyl borate, diethyl borate, dibutylborate, and diethylhexyl borate; a diester borate such as dibenzylborate and diphenyl borate; and a triester borate such as tributylborate.

The thiophosphate above can include methyl thiophosphate, dimethylthiophosphate, trimethyl thiophosphate, ethyl thiophosphate, diethylthiophosphate, triethyl thiophosphate, propyl thiophosphate, dipropylthiophosphate, tripropyl thiophosphate, butyl thiophosphate, dibutylthiophosphate, tributyl thiophosphate, hexyl thiophosphate, dihexylthiophosphate, trihexyl thiophosphate, octyl thiophosphate, dioctylthiophosphate, trioctyl thiophosphate, ethylhexyl thiophosphate,diethylhexyl thiophosphate, triethylhexyl thiophosphate, benzylthiophosphate, dibenzyl thiophosphate, tribenzyl thiophosphate, phenylthiophosphate, diphenyl thiophosphate, triphenyl thiophosphate, decylthiophosphate, didecyl thiophosphate, tridecyl thiophosphate, dodecylthiophosphate, didodecyl thiophosphate, and tridodecyl thiophosphate.Among the thiophosphates above, particularly preferable are for example,a dialkyl thiophosphate such as dimethyl thiophosphate, diethylthiophosphate, dipropyl thiophosphate, dibutyl thiophosphate, anddiethylhexyl thiophosphate; a diester thiophosphate such as dibenzylthiophosphate and diphenyl thiophosphate; and a truster thiophosphatesuch as tributyl thiophosphate.

The dithiophosphate above can include methyl dithiophosphate, dimethyldithiophosphate, trimethyl dithiophosphate, ethyl dithiophosphate,diethyl dithiophosphate, triethyl dithiophosphate, propyldithiophosphate, dipropyl dithiophosphate, tripropyl dithiophosphate,butyl dithiophosphate, dibutyl dithiophosphate, tributyldithiophosphate, hexyl dithiophosphate, dihexyl dithiophosphate,trihexyl dithiophosphate, octyl dithiophosphate, dioctyldithiophosphate, trioctyl dithiophosphate, ethylhexyl dithiophosphate,diethylhexyl dithiophosphate, triethylhexyl dithiophosphate, benzyldithiophosphate, dibenzyl dithiophosphate, tribenzyl dithiophosphate,phenyl dithiophosphate, diphenyl dithiophosphate, triphenyldithiophosphate, decyl dithiophosphate, didecyl dithiophosphate,tridecyl dithiophosphate, dodecyl dithiophosphate, didodecyldithiophosphate, and tridodecyl dithiophosphate. Among thedithiophosphates above, particularly preferable are, for example, adialkyl dithiophosphate such as dimethyl dithiophosphate, diethyldithiophosphate, dipropyl dithiophosphate, dibutyl dithiophosphate, anddiethylhexyl dithiophosphate; a diester dithiophosphate such is dibenzyldithiophosphate and diphenyl dithiophosphate; and a triesterdithiophosphate such as tributyl dithiophosphate.

Among these phosphoric acid, phosphate, phosphorous acid, phosphite,boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoricacid, dithiophosphate, particularly preferable example includephosphate, phosphite, thiophosphate, and dithiophosphate. Among them,further particularly preferable example includes diester phosphate,diester phosphite, diester thiophosphate, and diester dithiophosphate.In particular, diester phosphate and diester phosphite are preferable.

It is preferable that said at least one kind selected from the groupconsisting of phosphoric acid, phosphate, phosphorous acid, phosphite,boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoricacid and dithiophosphate is contained at an amount of 1 to 100% by massstandard with respect to the organic ferric sulfonate (namely, withrespect to 100 parts by mass of the organic ferric sulfonate, said atleast one kind selected from the group consisting of phosphoric acid,phosphate, phosphorous acid, phosphite, boric acid, borate,thiophosphoric acid, thiophosphate, dithiophosphoric acid anddithiophosphate is contained at an amount of 1 to 100 parts by mass).When the content of said at least one kind selected from the groupconsisting of phosphoric acid, phosphate, phosphorous acid, phosphite,boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoricacid and dithiophosphate is lower than the range above, the effect toreduce the leak current might not be enough. When the content of said atleast one kind selected from the group consisting of phosphoric acid,phosphate, phosphorous acid, phosphite, boric acid, borate,thiophosphoric acid, thiophosphate, di thiophosphoric acid anddithiophosphate is higher than the range above, the ESR might be high,or the characteristic under a high temperature and a high humidity mightbe deteriorated. In particularly, with respect to the organic ferricsulfonate, said at least one kind selected from the group consisting ofphosphoric acid, phosphate, phosphorous acid, phosphite, boric acid,borate, thiophosphoric acid, thiophosphate, dithiophosphoric, acid anddithiophosphate is preferably contained at an amount of 1.5% or more bymass standard. More preferably, it is 3% or more. Also, it is preferably20% or less, and more preferably, it is 15% of less, and yet norepreferably is 10% or less.

By contrast, the organic sulfonic acid for th eorganic ferric sulfonatecan include: for example, an aromatic sulfonic acid such asbenzenesulfonic acid or its derivative, naphthalenesulfonic acid or itsderivative, and anthraquinonesulfonic acid or its derivative; polymericsulfonic acid such as polystyrene acid, sulfonated polyester,phenolsulfonic acid novolac resin, and a copolymer of styrenesulfonicacid and non-sulfonic acid type monomer as detailed later; and achain-shaped sulfonic acid such as methanesulfonate ethanesulfonic acid,propanesulfonic acid and butane-sulfonic acid.

In particular, the aromatic sulfonic acid is easy to produce electrolytecapacitors having superior capacitor characteristics such as law ESR andhigh capacitance, and also can be used alone. Therefore, it ispreferably used as an organic sulfonic acid to constitute the organicferric sulfonate. By contrast, the chain-shaped sulfonic acid such asmethanesulfonic acid ethanesulfonic acid, propanesulfonic acid andbutane sulfonic acid has an acidity higher than the aromatic sulfonicacid, and therefore, it is preferable to be used together with thearomatic sulfonic acid rather than being used alone. In other words, thearomatic sulfonic acid can appropriately cause reaction at a lowhumidity (a humidity of approximately less than 35%) to easily produce aconductive polymer with good characteristics, but it has a property thatthe reaction does not tend to be progressed at a high humidity (ahumidity of approximately 50% or more). Therefore, it can beappropriately modified by strong acidity of the chain-shaped sulfonicacid, thereby progressing the reaction.

Regarding the benzenesulfonic acid and its derivative, the examples ofthe benzenesulfonic acid derivative can include toluenesulfonic acid,ethylbenzenesulfonic acid, propylbenzenesulfonic acid,butylbenzenesulfonic acid, dodecylbenzenesulfonic acid,methoxybenzenesulfonic acid, ethoxybeazenesulfonic acid,propoxybenzenesulfonic acid, butoxybenzenesulfonic acid, phenolsulfonicacid, cresolsulfonic acid, and benzenedisulfonic acid. Regarding thenaphthalenesulfonic acid and its derivative, the examples of thenaphthalenesulfonic acid derivative can include naphthalenedisulfonicacid, naphthalenetrisulfonic acid, methylnaphthalenesulfonic acid,ethylnaphthalenesulfonic acid, propylnaphthalenesuifonic acid, andbutylnaphthalenesulfonic acid. Regarding the anthraquinonesulfonic acidand its derivative, the examples of the anthraquinonesulfonic acidderivative can include anthraquinonedisulfonic acid, andanthraquinonetrisulfonic acid. Among these aromatic sulfonic acids,preferable are toluenesulfonic acid, methoxybenzenesulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid, andnaphthalenetrisulfonic acid. Particularly preferable arep-toluenesulfonic acid, methoxybenzenesulfonic acid, andnaphthalenesulfonic acid. Specifically, naphthalenesulfonic acid ispreferable.

The aromatic sulfonic acid above can be used alone, or in combination oftwo kinds or more. When two kinds or more are used together, it ispreferable that one of the aromatic sulfonic acids isnaphthalenesulfonic acid. Favorable example of using two kinds or morecan include a combination of naphthalenesulfonic acid andmethanesalfonic acid, and a combination of naphthalenesulfonic acid andp-toluenesulfonic acid.

It is preferable that the organic ferric sulfonate has a molar ratio ofiron to an organic sulfonic acid, wherein the molar ratio is lower than1:3 in view of the organic sulfonic acid. Namely, it is to reduce themolar ratio of the sulfonic acid organic below 1:3, that is, thestoichiometric molar ratio of he organic sulfonic acid with respect toiron, thereby slightly reducing the reaction rate of the organic ferricsulfonate. The molar ratio of the organic sulfonic acid with respect toiron is preferably about 1:2 or less. It is further preferably about1:2.2 or less. Specifically, it is preferably about 1:2.4 or less. Yetspecifically, it is preferably about 1:2.75 or less.

The oxidant dopant agent for conductive polymer preparation above can beused as it is, namely in a solid state such as powders. However, inproducing the conductive polymer, it is preferable that the oxidantdopant agent for conductive polymer preparation is dissolved in water,an alcohol, or a mixtures of water and an alcohol, so as to be providedas a solution. As a result, the handling property can be improved bymaking it a solution while the state with monomers can become morehomogeneous, thereby showing the function as an oxidant dopant agentmore effectively.

As the alcohol to be used as the solvent as mentioned above, theexamples can include monovalent alcohol such as methanol (methylalcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), butanol(butyl alcohol), and polyalcohol such as ethylene glycol, propyleneglycol, diethylene triethylene glycol and polyethylene glycol. Amongthem, preferable is a monovalent alcohol having carbon number of 1 to 4,including methanol ethanol propanol and butanol.

It is preferable that the concentration of the oxidant dopant agent forconductive polymer preparation (which may be hereinafter simplified as“oxidant dopant agent”) is 20 to 70 mass % in the solution of theoxidant dopant agent for conductive polymer preparation. When theconcentration of the oxidant dopant agent is lower than 20 mass %, theoxidation power might become weak, and therefore, the polymerization ofthe monomers might not progress enough. When the concentration of theoxidant dopant agent is higher than 70 mass %, the viscosity mightbecome too high to soak into the capacitor element, and therefore, itmight become difficult to produce capacitors. In the range of 20 to 70mass % for the concentration of the oxidant dopant agent in the oxidantdopant agent solution mentioned above, it is more preferably 25 mass %more, and further more preferably 30 mass %, or more, and in addition,it is more preferably 65 mass % or less, and further more preferably 60mass % or less.

The oxidant dopant agent for conductive polymer preparation isconstituted by including an organic ferric sulfonate, and at least onekind selected from the group consisting of phosphoric acid, phosphate,phosphorous acid, phosphite, boric acid, borate, thiophosphoric acid,thiophosphate, dithiophosphoric acid and dithiophosphate. As a result,an electrolyte capacitor with low leak current can be provided.Furthermore, a glycidyl group containing compound (in other words, epoxygroup) or its ring-opening compound can be added. Then, in addition tothe characteristic of low leak current as mentioned above, anelectrolyte capacitor further provided with high breakdown voltage (inother words, the withstanding voltage property is superior) can beproduced.

The suitable examples of the glycidyl group containing compound caninclude a monoglycidyl compound represented by general formula (1); adiglycidyl compound represented in general formula (2); a diglycidylcompound represented in general formula (3); glycerin diglycidyl ether,diglycerine tetraglycidyl ether, alcohol-soluble epoxy resin andalcohol-soluble polyglycerin polyglycidyl, and the ring-openingcompounds thereof; and epoxy polysiloxane (“polysiloxane “means” acompound having two or more siloxane bonds”) and its ring-openingcompound.

(In the formula, R¹ represents hydroxyl group, an alkyl group having acarbon lumber of 1 to 5 or an alkoxy group having a carbon number of 1to 7.)

(In the formula, R² represents an alkylene group having a carbon numberof 2 to 6.)

(In the formula. R³ represents an alkylene group having a carbon numberof 2 to 3, and n represents 2 to 20.)

The glycerin diglycidyl ether above is represented by general formula(4).

The diglycerine tetraglycidyl ether above is represented by generalformula (5).

The ring-opening compounds of the monoglycidyl compound represented bygeneral formula (1), the diglycidyl compound represented in generalformula (2), the diglycidyl compound represented in general formula (3),glycerin diglycidyl ether, diglycerine tetraglycidyl ether, and etc.have the structure below. The glycidyl group of the compound havingthose glycidyl group are ring-opened to become a glycol represented bygeneral formula (6).

Those such as monoglycidyl compound represented by general formula (1),the diglycidyl compound represented in general formula (2), thediglycidyl compound represented in general formula (3), glycerindiglycidyl ether, diglycerine tetraglycidyl ether and etc. are compoundshaving 1 to 4 glycidyl groups. In the present invention, the compoundhaving 1 to 4 glycidyl groups or its ring-opening compound can besuitably used. However, as the glycidyl group containing compound or itsring-opening compound in the present invention, in addition to thecompound having 1 to 4 glycidyl groups or its ring-opening compound asmentioned above, it is also possible to use alcohol-soluble epoxy resinor its ring-opening compound, alcohol-soluble polyglycerin polyglycidylor its ring-opening compound, and epoxy polysiloxane or its ring-openingcompound. As the alcohol-soluble epoxy resin, for example, acommercially available product with the product name, “WATER SOLBC-3010” from DIC Corporation, can be suitably used. As thealcohol-soluble polyglycerin polyglycidyl, for example, a commerciallyavailable product with the product name, “SR-4GLS” from Sakamoto YakuhinKogyo Co., Ltd., can be suitably used. As the epoxy polysiloxane above,for example, a commercially available product with product name such as“X-41-1053, X-41-1056,” or “X-41-1059A” from Shin-etsu Chemistry Co.,Ltd. can he suitably used. The ring-opening compounds of thesealcohol-soluble epoxy resin, alcohol-soluble polyglycerin polyglycidyl,epoxy polysiloxane, and etc. are due to the reaction of ring-opening ofthe glycidyl groups, so as to become a glycol as represented by generalformula (6) above.

In case where the glycidyl group containing compound has two or moreglycidyl groups, the ring-opening compound of all the glycidyl groups donot necessarily ring-opened, but it is possible that only a part thereofcan be ring-opened.

Here, regarding the monoglycidyl compound as represented by generalformula (1) and its ring-opening compound, the specific examples caninclude epoxy propanol (i.e., glycidol), methyl glycidyl ether, ethylglycidyl ether, propyl glycidyl ether, butyl glycidyl ether, epoxybutane(i.e., glycidyl methane) epoxypentane (i.e., glycidyl ethane),epoxyhexane (i.e., glycidyl propane), epoxyheptane (i.e., glycidylbutane), epoxyoctane (i.e., glycidyl pentane),glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane,glycidoxypropyltriethoxysilane, glycidoxypropylmethyldethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and glycidyl methacrylate.In particular, epoxy propanol, butyl glycidyl ether, epoxybutane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferable.

The examples of the diglycidyl compound represented by general formula(2) can include ethylene glycol diglycidyl ether, propylene glycoldiglycidyl ether, butylene glycol diglycidyl ether, pentylene glycoldiglycidyl ether, hexylene glycol diglycidyl ether, and glycerindiglycidyl ether. In particular, ethylene glycol diglycidyl ether andpropylene glycol diglycidyl ether are preferable.

The examples of the diglycidyl compound represented by general formula(3) can include diethylene glycol diglycidyl ether, dipropylene glycoldiglycidyl ether, triethylene glycol diglycidyl ether, tripropyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, andpolypropylene glycol diglycidyl ether. In particular, polyethyleneglycol diglycidyl ether is preferable.

The glycidyl group containing compound or its ring-opening compound, asmentioned above can be used alone, or in combination of two or morekinds.

The glycidyl group containing compound or its ring-opening compound asmentioned above can include ones having a high boiling point (forexample, ethylene glycol diglycidyl ether has a boiling point of 112°C./0.6 kPa). They might not be able to be removed by normal dryingprocess and can be left in the conductive polymer. However, even if itis left therein, the Examples described later show that it does notresult in an increase of the ESR or a drop of the capacitance, norbrings about a drop of the withstanding voltage property.

The glycidyl group containing compound or ring-opening compound can beadded at the following content with respect to the organic ferricsulfonate. That is, it is preferably added at a content of 5 to 100% bymass standard (i.e., 5 to 100 parts by mass of the glycidyl groupcontaining compound or its ring-opening compound are added to 100 partsby mass of the organic ferric sulfonate). When the content of theglycidyl group containing compound or its ring-opening compound is lowerthan the range above, the function to enhance the withstanding voltageproperty cannot be sufficiently given. By contrast, when the content ofthe glycidyl group containing compound or its ring-opening compound ismore than the range above, the effects obtained by increasing thecontent can be given little. In addition, the costs might be raisedwhile it can be non-miscible, and the stability of the oxidant dopantagent solution can be deteriorated. Also, the glycidyl group containingcompound or its ring-opening compound with respect to the organic ferricsulfonate can be added as follow. Namely, within the range discussedabove, it can be added by mass standard at a content of 10 mass % ormore, and more preferably at a content of 14% or more, and also, it canbe added at a content of 40% or less, and more preferably at a contentof 36% or less.

When the polyalcohol is further added into the oxidant dopant agentsolution including the compound having glycidyl group or itsring-opening compound above, the effects to improve the withstandingvoltage property based on the addition of the compound having glycidylgroup or its ring-opening compound can be further enhanced, andfurthermore, the ESR can be reduced more.

The polyalcohol to be used is preferably one including an aliphatichydrocarbon having a carbon number of 2 to 10 further attaching 2 to 3hydroxy groups thereto. The specific examples of the polyalcohol caninclude ethylene glycol, propanediol, butanediol, pentanediol,hexanediol, heptanediol, octanediol, nonanediol, decanediol glycerol andetc. In particular, glycerol, ethylene glycol, propanediol, andbutanediol are preferable.

Regarding the content of the polyalcohol in the oxidant dopant agentsolution, it is preferable that the polyalcohol is added by massstandard at a content of 20% or less with respect to the organic ferricsulfonate (i.e., the polyalcohol is added 20 parts by mass or less withrespect to 100 parts by mass of the organic ferric sulfonate). Althoughthe effects by the polyalcohol addition can be increased depending onthe quantity even if it is added at a small quantity. However, in orderto give the effect more clearly, it is preferable that the polyalcoholis added by mass standard at a content of 4% or more with respect to theorganic ferric sulfonate. Also, as the content of the polyalcohol isincreased, the viscosity of the oxidant dopant agent solution can beincreased. Therefore, it is preferable that the polyalcohol is added ata content of 20% or less by mass standard with respect to the organicferric sulfonate.

The order of the addition of the glycidyl group containing compound orits ring-opening compound and the polyalcohol is not particularlylimited. They can be added concurrently, or one can be add before theother is added.

In the present invention, the monomer to synthesize the conductivepolymer can include thiophene or its derivative, pyrrole or itsderivative, and aniline or its derivative. In particular, thiophene orits derivative can be preferably used. As explained before, theconductive polymer obtained by polymerising thiophene or its derivativecan be provided with a balanced feature in the conductivity and the heatresistance, and therefore, it can be possible to obtain an electrolytecapacitor more excellent in the capacitor properties than any othermonomers.

Regarding thiophene or its derivative, the examples of the derivative ofthiophene can include 3,4-ethylenedioxythiophene, 3-alkylthiophene,3-aroxythiophene, 3-alkyl-alkoxythiophene, 3,4-alkylthiophene and 3,4-alkoxythiophene, and alkylated ethylenedioxythiophene which hasmodified 3,4 -ethyleneioxythiophene with an alkyl group. Here, the alkylgroup and alkoxy group can preferably have a carbon member of 1 to 16,and more preferably it has 1 to 10, and yet more preferably it has 1 to4.

Further explanation is made for the alkylated ethylenedioxy thiophene inwhich 3,4-ethylenedioxy thiophene is modified with an alkyl group.3,4-ethylenedioxy thiophene and the alkylated ethylenedioxy thiophene asmentioned above correspond to a compound represented by the followingformula (7).

(In the formula, R⁴ is hydrogen or an alkyl group.)

In the formula (7) mentioned above, when R⁴ is hydrogen, it is3,4-ethylenedioxythiophene. When it is expressed by the IUPAC name, itis 2,3-dihydro-thieno[3,4-b][1,4]dioxine. However, this compound isoften expressed by its common name, “3,4-ethylenedioxythiophene,” ratherthen the IUPAC name. Therefore, this specification refers it as “3,4-ethylenedioxythiophene” rather than“2,3-dihydro-thieno[3,4-b][1,4]dioxine.” Also, when R⁴ in the formula(7) is an alkyl group, this alkyl group is preferably of a carbon numberof 1 to 10. In particular, one with a carbon number of 1 to 4 ispreferable. Namely, the alkyl group is preferably methyl group, ethylgroup, propyl group, or butyl group. Specifically, when R⁴ in formula(7) is methyl group, such a compound is expressed as“2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine” under the IUPAC name,which is hereinafter simply referred to as “methylatedethylenedioxythiophene.”When R⁴ in formula (7) is ethyl group, such acompound is “2-ethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine” under theIUPAC name. Hereinafter, this compound is simply referred to as“ethylated ethylenedioxythiophene.”

When R⁴ in formula (7) is propyl group, such a compound is“2propyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine” under the IUPAC name.Hereinafter, this compound is simply referred to as “propylatedethylenedioxythiophene.” Also, when R⁴ in formula (7) is butyl group,such a compound is “2-butyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine” underthe IUPAC name. Hereinafter, this compound is simply referred to as“butylated ethylenedioxythiophene.” In addition,“2-alkyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine” is simply referred to as“alkylated ethylenedioxythiophene.” Here, among the alkylatedethylenedioxy thiophenes, particularly preferable are methylatedethylenedioxythiophene, ethylated ethylenedioxy thiophene, propylatedethylenedioxythiophene, and butylated ethylenedioxythiophene.

Also, it is preferable that 3,4-ethylenedioxythiophene (namely,2,3-dihydro-thieno[3,4-b][1,4] dioxine) and the alkylatedethylenedioxythiophene (namely,2-alkyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine) are mixed together foruse. The mixture ratio is at a molar ratio of 0.05:1 to 1:0.1.Particularly, it is 0.1:1 to 1:0.1. More particularly, it is 0.2:1 to1:0.2. Yet more preferably, it is 0.3:1 to 1:0.3.

The oxidant dopant agent for conductive polymer preparation isconstituted by including an organic ferric sulfonate, and at least onekind selected from the group consisting of phosphoric acid, phosphate,phosphorous acid, phosphite, boric acid, borate, thiophosphoric acid,thiophosphate, dithiophosphoric acid and dithiophosphate. Alternatively,it can be constituted b including the inevitable two elements above, incombination of a glycidyl group containing compound or its ring-openingcompound. In addition, a silane coupling agent, polysiloxane, and apolymer or a polymerized compound such as alcohol-soluble resin andpolyethylene glycol can be added.

The production of the conductive polymer by using the oxidant dopantagent solution of the present invention is applicable to both normalproduction of the conductive polymer, and the production of theconductive polymer at the time of producing electrolyte capacitors, thatis, so called “on-site polymerization.”

The monomer such as thiophene or its derivative is liquid at roomtemperature, so that it can be used as it is for polymerization. Also,in order to more smoothly progress the polymerization reaction, themonomer can be diluted with an organic solvent such as methanol,ethanol, propanol, butanol, acetone and acetonitrile to make it anorganic solvent solution. Note that the explanation here is made forthiophene or its derivative as a monomer, since it is particularlypreferable embodiment. However, pyrrole or its derivative, and anilineor its derivative can be used in the same manner as thiophene or itsderivative, as well.

In case of the normal production of the conductive polymer (the normalproduction of the conductive polymer means that it is not, so-called,the “on-site polymerization,” that is, the production of the conductivepolymer at the time of producing electrolyte capacitors) a mixture ofthe oxidant dopant agent solution of the present invention and thiopheneor its derivative as a monomer is used (the mixture ratio of the oxidantdopant agent and monomer is preferably from 5:1 to 15:1 by massstandard). For example, an oxidation polymerization is performed at 5 to95° C. for 1 to 72 hours.

As described above, the oxidant dopant agent of the present invention isanyway mixed with a monomer when producing an electrolyte capacitor.Therefore, regarding the oxidant dopant agent, the organic ferricsulfonate is not necessarily mixed with said at least one kind selectedfrom the group consisting of phosphoric acid, phosphate, phosphorousacid, phosphite, boric acid, borate, thiophosphoric acid, thiophosphate,dithiophosphoric acid and dithiophosphate, so as to provide the oxidantdopant agent prior to mixing it with a monomer. Instead, the same stateabove can be made if the organic ferric sulfonate is concurrently mixedwith a monomer and said at least one kind selected from the groupconsisting of phosphoric acid, phosphate, phosphorous acid, phosphite,boric acid, borate, thiophosphoric acid, thiophosphate, dithiophosphoricacid and di thiophosphate, thereby providing a mixture of the oxidantdopant agent including the monomer. Moreover, the same state above canbe also made when a monomer is mixed with said at least one kindselected from the group consisting of phosphoric acid, phosphate,phosphorous acid, phosphite, boric acid, borate, thiophosphoric acid,thiophosphate, dithiophosphoric acid and dithiophosphate, into which theorganic ferric sulfonate is then added, thereby providing a mixture ofthe oxidant dopant agent including the monomer. Therefore, in producingthe electrolyte capacitor, the oxidant dopant agent of the presentinvention can be prepared in either way as explained above.

The oxidant dopant agent solution of the present invention wasparticularly developed for so-called “on-site polymerization” at thetime of production of electrolyte capacitors by producing a conductivepolymer of a monomer, thiophene or its derivative. Therefore, theexplanation is made for such an embodiment.

Also, the electrolyte capacitors can include aluminum electrolytecapacitor, tantalum electrolyte capacitor, niobium electrolytecapacitor, and etc. Among aluminum electrolyte capacitors, there are awinding-type aluminum electrolyte capacitor, and a laminated-type orflat type aluminum electrolyte capacitor. Since the oxidant dopant agentsolution of the present invention can be applicable to the production ofthe winding-type aluminum electrolyte capacitor, such an example isfirst explained.

First, as the capacitor element for the winding-type aluminumelectrolyte capacitor, a surface of an aluminum foil is applied to anetching treatment followed by carrying out a conversion treatment,thereby forming a positive electrode having a dielectric layer, to whicha lead terminal is attached. Also, a lead terminal is attached to anegative electrode made of an aluminum foil. These positive electrodeand negative electrode having lead terminals are wound together with anintervention of a separator, thereby forming a favorable capacitorelement.

Then, the following is an example when producing the winding-typealuminum electrolyte capacitor by using the capacitor element mentionedabove. Namely, the capacitor element above is immersed in a mixture ofthe oxidant dopant agent solution of the present invention including amonomer (thiophene or its derivative), and then it is pulled up (takenout). Then, at room temperature or under heating, the monomer ispolymerized to form an electrolyte layer made of a conductive polymerhaving a polymer backbone of a polymer of thiophene or its derivative.Then, the capacitor element having the electrolyte layer is surroundedby an exterior material to provide a winding-type aluminum electrolytecapacitor.

Alternatively, instead of immersing the capacitor element in the mixtureof oxidant dopant agent solution of the present invention, and amonomer, the following method can be adopted. The monomer is dilutedwith the organic solvents such as methanol, as explained before. Then,the capacitor element is immersed in the monomer solution, and pulled upfor drying. Then, the capacitor element is immersed in the oxidantdopant agent solution of the present invention, and then, it is pulledup. Then, the monomer is polymerized at room temperature or underheating. Or, the capacitor element is first immersed in the oxidantdopant agent solution of the present invention, and then, it is pulledup for drying. The capacitor element is then immersed in a monomer, andpulled up, followed by polymerizing the monomer at room temperature orunder heating. Then, a winding-type aluminum electrolyte capacitor canbe prepared in the same manner as explained before.

Other than the winding-type aluminum electrolyte capacitor as mentionedabove, the electrolyte capacitor such as a laminated-type or flat typealuminum electrolyte capacitor, tantalum electrolyte capacitor, orniobium electrolyte capacitor can be prepared as follow. The capacitorelement used is a positive electrode made of a porous body of a valvemetal such as aluminum, tantalum, niobium, and etc. and a dielectricfilm of an oxidation film of the valves metal. In the same manner as thewinding-type aluminum electrolyte capacitor, the capacitor element isimmersed in the mixture of the oxidant dopant agent solution of thepresent invention and a monomer, and then it is pulled up, followed bypolymerizing the monomer at room temperature or under heating. Or, thecapacitor element is immersed in a monomer solution and pulled up fordrying, which is then immersed in the oxidant dopant agent solution ofthe present invention and pulled up, followed by polymerizing themonomer at room temperature or under heating. Or, the capacitor elementis immersed in the oxidant dopant agent solution of the presentinvention and pulled up for drying, which is then immersed in as monomersolution and pulled up, followed by polymerizing the monomer at roomtemperature or under heating, and then the capacitor element is washedand dried. Then, the process is repeated to form an electrolyte layermade of a conductive polymer, followed by applying carbon paste andsilver paste. Then, it is dried and surrounded on its outer surface,thereby providing a laminated-type or flat type aluminum electrolytecapacitor, tantalum electrolyte capacitor, niobium electrolytecapacitor, and etc.

In addition, the explanation above involves the immersion of thecapacitor element. That is, the capacitor element is immersed in themixture of the oxidant dopant agent solution of the present inventionand the monomer, or it is immersed in the monomer solution, or it isimmersed in the oxidant dopant solution of the present invention.However, the capacitor element can be sprayed to apply it to impregnatewith it.

In the production of the conductive polymer, or in the production of theconductive polymer to produce the electrolyte capacitor by “on-sitepolymerization,” the following is preferable. Regarding the use ratio ofthe oxidant dopant agent solution of the present invention, and themonomer (thiophene or its derivative) or the monomer solution monomer,the mass ratio of the organic ferric sulfonate to become the oxidantdopant agent and the monomer is preferably from 2:1 to 8:1. The “on-sitepolymerization” can be performed, for example, at 10 to 300° C. for 1 to180 minutes.

Also, in the production of the electrolyte capacitor, a conductivepolymer by using oxidant dopant agent solution of the present inventionis formed, and then, on the conductive polymer, a conductive polymerlayer is formed by using a π conjugated system conductive polymerdispersion liquid. That is, electrolyte is constituted by both, therebyproviding an electrolyte capacitor.

The π conjugated system conductive polymer that can be used is a πconjugated system conductive polymer using a polymer anion as a dopant.

The polymer anion is mainly comprised of a polymeric sulfonic acid. Sucha polymer anion is explained in detail. The examples of the polymeranion can include polystyrene sulfonic acid, sulfonated polyester,phenolsulfonic acid novolac resin, and a copolymer of styrenesulfonicacid and a non-sulfonic acid system monomer.

Regarding the polystyrene sulfonate above, its weight average molecularweight can be preferably 10,000 to 1,000,000.

Namely, when the weight average molecular :weight of the polystyrenesulfonic acid above is smaller than 10,000, thereby obtained conductivepolymer might have a low conductivity. By contrast, when the weightaverage molecular weight of the polystyrene sulfonate above is largerthan 1,000,000, the viscosity of the dispersion liquid of the conductivepolymer becomes high, and therefore, it might be difficult to handle itin the production of an electrolyte capacitor. Furthermore, within therange of the weight average molecular weight of the polystyrene sulfonicacid mentioned above, it is preferably 20,000 or more, and morepreferably 40,000 or more, and also, it is preferably 800,000 or less,and more preferably 300,000 or loss.

The sulfonated polyester above can be obtained by condensationpolymerization from a dicarbozybenenesulfonic acid diester such assulfoisophthalate and sulfoterephthalate and an alkylene glycol in thepresence of a catalyst such as antimony oxide or zinc oxide. The weightaverage molecular weight of the sulfonated polyesters can be preferably5,000 to 300,000.

Namely, when the weight average molecular weight of the sulfonatedpolyester is lower than 6,000, thereby obtained conductive polymer mighthave a low conductivity. Also, when the weight average molecular weightof the sulfonated polyester above is larger than 300,000, the viscosityof the dispersion liquid of the conductive polymer becomes high, andtherefore, it might be difficult to handle it in the production of anelectrolyte capacitor. Furthermore, within the range of the weightaverage molecular weight of the sulfonated polyester above, it ispreferably 10,000 or more, and more preferably 20,000 or more, and also,it is preferably 100,000 or less, and more preferably 80,000 or less.

Also, the weight average molecular weight of the phenolsulfonic acidnovolac resin can be preferably 5,000 to 500,000.

Namely, when the weight average molecular weight of the phenolsulfonicacid novolac resin above is smaller than 5,000, thereby obtainedconductive polymer might be low in the conductivity. By contrast, whenthe weight average molecular weight of the phenolsulfonic acid novolacresin above is larger than 500,000, the viscosity of the dispersionliquid of the conductive polymer becomes high, and therefore, it mightbe difficult to handle it in the production of an electrolyte capacitor.Furthermore, within the range of the weight average molecular weight ofthe phenolsulfonic acid novolac resin above, it is preferably 10,000 ormore, and also, it is preferably 400,000 or less, and more preferably80,000 or less.

The polymer anion such as polystyrene sulfonic acid, sulfonatedpolyester, and phenolsulfonic acid novolac resin as mentioned above canbe used alone or in combination of two kinds or more.

A copolymer made from styrenesulfonic acid, and at least one kind of anon-sulfonic acid monomer selected from the group of methacrylate,acrylate, and unsaturated hydrocarbon containing alkoxysilane compoundor its hydrolysate (which can be hereinafter referred to as “copolymerof styrenesulfonic acid and non-sulfonic acid monomer”) is used as adopant. Thereby obtained conductive polymer of thiophene or itsderivative obtained by oxidation polymerization has a high conductivityand superior heat resistance. Therefore, it is suitable to manufacturean electrolyte capacitor which is low in the ESR, reliable under a hotcondition, and causes less leakage current.

There is provided an explanation of the polymerization of the copolymerfrom styrenesulfonic acid, and at least one kind of a non-sulfonic acidmonomer selected from the group consisting of methacrylate, acrylate,and unsaturated hydrocarbon containing alkozysilane compound or ahydrolysate thereof. The monomer to be copolymerized with thestyrenesulfonic acid is at least one kind of a non-sulfonic acid monomerselected from the group of methacrylate, acrylate, and unsaturatedhydrocarbon containing alkoxysilane compound or a hydrolysate thereof.The examples of the methacrylate as mentioned above can include methylmethacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, hexyl methacrylate, stearyl methacrylate, cyclohexylmethacrylate, diphenylbutyl methacrylate, dimethylaminoethylmethacrylate, diethylaminoethyl methacrylate, sodium sulfohexylmethacrylate, glycidylmethacrylate, methylglycidylmethacrylate,hydroxyalkyl methacrylate, (namely, hydroxyalkyl methacrylate such ashydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate,hydroxystearyl methacrylate), hydroxypolyoxyethylene methacrylate, methoxyhydroxypropyl methacrylate, ethoxyhydroxypropyl methacrylate,dihydroxypropyl methacrylate, and dihydroxybutyl methacrylate. Inparticular, preferable are hydroxyalkyl methacrylate such ashydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate and hydroxybutyl methacrylate. The carbon number of thesecompounds is 1 to 4. It is preferable to show a characteristic servingas a dopant when it is copolymerized with styrenesulfonic acid. Also,the compounds such as glycidyl methacrylate and methylglycidyltethacrylate include a glycidyl group. These compounds have a structurehaving hydroxyl group when opening the glycidyl group. Therefore, in thesame reasons as the hydroxyalkyl methacylate, a glycidyl groupcontaining compound is also preferable in view of the characteristicserving as a dopant when it is copolymerised with styrenesulfonic acid.

Also, the examples of the acrylate as mentioned above can include methylacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexylacrylate, stearyl acrylate, cyclohexyl acrylate, diphenylbutyl acrylate,dimethylaminoethyl acrylate, diethylaminoethyl acrylate, sodiumsulfohexyl acrylate, glycidyl acrylate, methylglycidylacrylate,hydroxyalkyl acrylate, (namely, hydroxyalkyl acrylate such ashydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate,and hydroxybutyl acrylate). In particular, preferable are hydroxymethylacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutylacrylate. The carbon number of these compounds is 1 to 4. Thesecompounds are preferable in view of the characteristic serving as adopant when it is copolymerized with styrenesulfonic acid. Also, thecompounds such as glycidyl acrylate and methylglycidyl acrylate includea glycidyl group. These compounds have a structure having hydroxyl groupwhen opening the glycidyl group. Therefore, in the same reasons as thehydroxyalkyl acrylate, a glycidyl group containing compound is alsopreferable in view of the characteristic serving as a dopant when it iscopolymerized with styrenesulfonic acid.

As the unsaturated hydrocarbon containing alkoxysilane compound or itshydrolysate as mentioned above, the followings can be exemplified. Thatis, the examples thereof can include an unsaturated hydrocarboncontaining alkoxysilane compound and its hydrolysate such as3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyldimethylmethoxysilane,3-methacryloxypropyldimethylethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyitrimethoxysilane,3-acryloxymethyldimetboxysilane, 3-acryloxymethyldethoxysilane,3-acryloxytriethoxysilane, p-styryitrimethoxysilane,p-styryltriethoxysilane, p-styrylmethyldimethoxysilanevinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane,and vinylmethyldimethoxysilane. The hydrolysate of such an unsaturatedhydrocarbon containing alkoxysilane compound can be as follows. Forexample, if the unsaturated hydrocarbon containing alkoxysilane compoundis 3-methacryloxypropyltrimethoxysilane as mentioned above, it can be acompound having as structure in which its methoxy group is hydrolyzed tobecome hydroxyl group (i.e., 3-methacryloxytrihydroxysilane), or acompound having a structure in which silane groups are condensed eachother to form an oligomer while its methoxy group that has not beeninvolved in the reaction becomes hydroxyl group. Also, as theunsaturated hydrocarbon containing alkoxysilane compound, favorable are3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane,p-styryltrimethoxysilane, and vinyltrimethoxysilane in view of servingas a dopant when it is copolymerized with styrenesulfonic acid.

Here, the following feature can be provided in the copolymer made fromstyrenesulfonic acid, and at least one kind of a non-sulfonic acidmonomer selected from the group consisting of methacrylate, acrylate,and unsaturated hydrocarbon containing alkoxysilane compound or itshydrolysate. A mass ratio of 1:0.01 to 0.1:1 is preferable for thestyrenesulfonic acid to said at least one kind of the non-sulfonic acidmonomer selected from the group of methacrylate, acrylate, andunsaturated hydrocarbon containing alkoxysilane compound or itshydrolysate.

Also, the following feature is found in the copolymer made fromstyrenesulfonic acid, and at least one kind of a non-sulfonic acidmonomer selected from the group of methacrylate, acrylate, andunsaturated hydrocarbon containing alkoxysilane compound or itshydrolysate. Regarding the molecular weight, it has a weight averagemolecular weight of about 5,000 to 500,000 in view of thecharacteristics of the water-solubility and the dopant. In particular,it preferably has a weight average molecular weight of about 40,000 to200,000.

The copolymer of the styrenesulfonic acid and the non-sulfonic acidmonomer above can be used together with a polymer anion such aspolystyrene sulfonic acid, sulfonated polyester, and phenolsulfonic acidnovolac resin, as mentioned above. Also, for use, a dispersion liquid ofa conductive polymer synthesized by using the copolymer from thestyrenesulfonic acid and the non-sulfonic acid monomer as a dopant canbe mixed with another dispersion liquid of a conductive polymersynthesized by using the polymeric sulfonic acid as a dopant.

Next, explained is the means to polymerize a conductive polymer by meansof oxidation polymerization of a monomer with a polymer anion as dopant(here, the most typical monomer, that is, thiophene or its derivative isexemplified). Listed here is polystyrene sulfonic acid, sulfonatedpolyester, phenolsulfonic acid novolac resin, and a copolymer ofstyrenesulfonic acid and a ion-sulfonic acid monomer e., a copolymerfrom styrenesulfonic acid and a non-sulfonic acid monomer selected fromthe group consisting of methacrylate, acrylate and an unsaturatedhydrocarbon containing alkoxysilane compound, and hydrolysate thereof).All of the lists above have solubility to water, or an aqueous solutionof a mixture of water and a water-miscible solvent. Thus, the oxidationpolymerization is performed in water or an aqueous solution.

As the water-miscible solvent constituting the aqueous solutionmentioned above, the examples thereof can include methanol, ethanol,propanol, acetone, and acetonitrile. The mixing ratio of thewater-miscible solvent with respect to water is preferably 50% by massor less.

The oxidation polymerization for preparing the conductive polymer can beeither through chemical oxidation polymerization or electrolyticoxidation polymerization.

To perform the chemical oxidation polymerization, a persulfate can beused as an oxidant, for example. The example of the persulfates caninclude ammonium persulfate, sodium persulfate, potassium persulfate,calcium persulfate, and barium persulfate.

Regarding the chemical oxidation polymerization, the condition duringthe polymerization is not particularly limited. The temperature in thechemical oxidation polymerization is preferably 5° C. to 95° C., and inmore particular, it is 10° C, to 30° C. The polymerization period ispreferably one hour to 72 hours, and more preferably, it is 8 hours to24 hours.

The electrolytic oxidation polymerization can he carried out either inconstant current or constant voltage. For example, when the electrolyticoxidation polymerization is performed in constant current, its currentvalue is preferably 0.05 mA/cm² to 10 mA/cm², and it is more preferably0.2 mA/cm² to 4 mA/cm². When the electrolytic oxidation polymerizationis performed in constant voltage, its voltage is preferably 0.5V to 10V,and it is more preferably 1.5V to 5V. The temperature at the time of theelectrolytic oxidation polymerization is preferably 5° C, to 95° C. andit is more preferably 10° C, to 30° C. The polymerization period ispreferably one hour to 72 hours, and it is more preferably 8 hours to 24hours. In addition, upon the electrolytic oxidation polymerization,ferrous sulfate or ferric sulfate can be added as a catalyst.

Just after the polymerization as prepared above, the conductive polymercan be obtained as a dispersion state in water or the aqueous solution,which includes a persulfate used as an oxidant, or an iron sulfate orits decomposition product used as a catalyst. Therefore, the dispersionliquid of the conductive polymer including the impurities can be appliedto a dispersion machine such as an ultrasonic homogenizer, high-pressurehomogenizer or planetary ball mill to disperse the impurities. Then, themetal components can be favorably removed by using a cation-exchangeresin. At this time, the particle size of the conductive polymermeasured by means of dynamic light scattering is preferably 100 μm orless, and it is more preferably 10 μm or less. Also, it is preferably0.01 μm or more, and it is more preferably 0.1 μm or more. Then, aprocess such as ethanol precipitation process, ultrafiltration processand anion exchange resin process can be applied to remove the compoundsgenerated by the decomposition of the oxidant and the catalyst.

In the present invention, the oxidant dopant agent for conductivepolymer preparation or its solution can be used to subject to oxidationpolymerization of a monomer such as thiophene or its derivative toprepare a conductive polymer, which is used as an electrolyte toconstitute an electrolyte capacitor. Or, both of the conductive polymerabove and another conductive polymer obtained by a π conjugated systemconductive polymer dispersion liquid including a polymer anion as adopant are used as an electrolyte to constitute an electrolytecapacitor, as well. Furthermore, a conductive auxiliary liquid can besoaked to constitute an electrolyte capacitor, in which the conductiveauxiliary liquid includes: a high boiling point organic solvent with asboiling point of 150° C. or more; or a high boiling point organicsolvent with a boiling point of 150° C. or more, and an aromaticcompound having at least one of hydroxyl group and carboxyl group.

Namely, the one conductive polymer is made by the oxidant dopant agentfor conductive polymer preparation or its solution which is subject tooxidation polymerization of a monomer such as thiophene or itsderivative. The other conductive polymer is obtained by a π conjugatedsystem conductive polymer dispersion liquid including a polymer anion asa dopant. Both of the one and the other conductive polymers can be usedas an electrolyte to constitute an electrolyte capacitor. As shown inExamples 118 to 119, such an embodiment had a lever leak current of theelectrolyte capacitor than the case which only one conductive polymerobtained from the oxidant dopant agent for conductive polymerpreparation or its solution to carry out the oxidation polymerization ofthe monomer such as thiophene or its derivative and use it as anelectrolyte to constitute an electrolyte capacitor. Also, an electrolytecapacitor can be provided with lower ESR and superior heat resistancewhen the conductive auxiliary liquid is soaked to constitute anelectrolyte capacitor, in which the conductive auxiliary liquidincludes: a high boiling point organic solvent with a boiling point of150° C. or more; or a high boiling point organic solvent with a boilingpoint of 150° C. or more, and an aromatic compound having at least oneof hydroxyl group and carboxyl group.

The conductive auxiliary liquid above can include a conductive solutionhaving a conductive (electric conductivity) lower than the conductivityof normal electrolyte liquid (usually the conductivity of 3 mS/cm ormore), or a solution having a conductivity equal to, or higher than, theelectrolyte liquid. By constituting an electrolyte capacitor havingsoaked with such a conductive solution, lower ESR and more superior heatresistance can be accomplished than the case in which a high boilingpoint organic solvent with a boiling point of 150° C. or more is soakedwithout the aromatic compound having at least one of hydroxyl group andcarboxyl group.

Even if the conductive auxiliary liquid above has a lower conductivitythan the electrolyte liquid, it can make the electrolyte capacitor havelower ESR and superior heat resistance. Numerically, it can be used ifit has a conductivity of 1 μS/cm or more, and preferably it has aconductivity of 5 μS/cm or more, and more preferably it has aconductivity of 8 μS/cm or more.

In the present invention, the conductivity of the conductive auxiliaryliquid can be measured at a temperature of 25° C., by using aconductivity measurement instrument (F-55) made by Horiba Seisakusho,Ltd. However, other conductivity measurement instrument equivalentthereto can be used to measure.

The conductive auxiliary liquid includes a high boiling point organicsolvent having a boiling point of 150° C. or more, and an aromaticcompound having at least one of hydroxyl group and carboxyl group.

The examples of the high boiling point organic solvent having a boilingpoint of 150° C. or more can include gamma-butyrolactone (boilingpoint=204° C.), butanediol (boiling point=230° C.), dimethylsulfoxide(boiling point=189° C.), sulfolane (boiling point=285° C.),N-methylpyrrolidone (boiling point=202° C.), dimethylsulfolane (boilingpoint=233° C.), ethylene glycol (boiling point=198° C.), diethyleneglycol (boiling point=244° C.), triethyl phosphate (boiling point=215°C.), tributyl phosphate (289° C.), triethylhexyl phosphate [215° C. (4mmHg)] and polyethylene glycol, which can be used alone or incombination of two or more. It is noted that some kinds of polyethyleneglycols do not have a boiling point under normal pressure, such aspolyethylene glycol 600 and polyethylene glycol 1500 (here, the numberjust after the term “polyethylene glycol” means its molecular weight).However, no kinds of polyethylene glycols boil at a temperature of 150°C. or less under normal pressure. In the present invention, polyethyleneglycols shall be included as a group of the solvents having a highboiling point.

Such a high boiling point organic solvent with a boiling point of 150°C. or more is used as a solvent to dissolve an aromatic compound havingat least one of hydroxyl group and carboxyl group in the conductiveauxiliary liquid of the present invention. The reasons why such anorganic solvent with such a high boiling point is used as a solvent inthe present invention are explained. Namely, the electrolyte capacitorcan be provided with lowers ESR and superior heat resistance asexplained above. Also, because of such a high boiling point, an increaseof internal pressure can be restricted at the time of the solderingduring the production of the electrolyte capacitor while volatilizationof the organic solvent can be also restricted for a long term.

Regarding the aromatic compound having at least one of hydroxyl groupand carboxyl group, the hydroxyl group is the group bonded to theconstitution carbons to make the aromatic ring, which is distinct fromthe —OH part included in the carboxyl group. The aromatic compoundhaving at least one of hydroxyl group and carboxyl group can includebenzene compounds, naphthalene compounds, and anthracene compounds. Theexamples thereof can include hydroxybenzene carboxylic acid,nitrophenol, dinitrophenol, trinitrophenol, aminonitrophenol,hydroxyanisole, hydroxydinitrobenzene, dihydroxydinitrobenzene,alkylhydroxyanisole, hydroxynitroanisole, hydroxynitrobenzene,carboxylic acid (i.e., hydroxynitrobenzoic acid), dihydroxynitrobenzenecarboxylic acid (i.e., dihydroxynitrobenzoic acid), phenol,dihydroxybenzene, trihydroxybenzene, dihydroxybenzene carboxylic acid,trihydroxybenzene carboxylic acid, hydroxybenzene dicarboxylic acid,dihydroxybenzene dicarboxylic acid, hydroxytoluene carboxylic acid,nitronaphthol, aminonaphthol, dinitronaphthol, hydroxynaphthalenecarboxylic acid, dihydroxynaphthalene carboxylic acid,trihydroxynaplithalene carboxylic acid, hydroxynaphthalene dicarboxylicacid, dihydroxynaphthalene dicarboxylic acid, hydroxyanthracene,dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene,hydroxyanthracene carboxylic acid, hydroxyanthracene dicarboxylic acid,dihydroxyanthracene dicarboxylic acid, tetrahydroxyanthracene dione,benzenecarboxylic acid, benzenedicarboxylic acid, naphthalenecarboxylicacid, and naphthalenedicarboxylic acid. These compounds can be usedalone or in combination of two or more.

The aromatic compound having at least one of hydroxyl group and carboxylgroup is used in constitution of the conductive auxiliary liquid in thepresent invention. Therefore, the aromatic compound having at least oneof hydroxyl group and carboxyl group has an ability to assist theelectronic conduction of the conductive polymer. In addition, it cansuppress the deterioration of the conductive polymer based on theantioxidant action of the aromatic compound.

In the conductive auxiliary liquid above, the high boiling point organicsolvent with a boiling point of 150° C, or more serves as a solvent, andthe aromatic compound having at least one of hydroxyl group and carboxylgroup serves as a solute. The concentration of the aromatic compoundhaving at least one of hydroxyl group and carboxyl group in theconductive auxiliary liquid is preferably 0.5-50 mass %. In particular,it is preferably 2 mass % or more; and further preferably it is 5 mass %or more; also, it is preferably 30 mass % or less; and yet morepreferably 20 mass % or less. In other words, when the concentration ofthe aromatic compound having at least one of hydroxyl group and carhoxylgroup is lower than the above range, the electrolyte capacitor might notresult in low ESR, nor improve the heat resistance. On the other hand,when the concentration of the aromatic compound having at least one ofhydroxyl group and carboxyl group is higher than the above range, thearomatic compound might precipitate, thereby making it difficult inhandling, as well as deteriorate the ESR of the electrolyte capacitor.

In addition, when the high boiling point organic solvent with a boilingpoint of 150° C. or more, or the conductive auxiliary liquid includes atleast one binder selected from the group of epoxy compound or itshydrolysate, silane or its hydrolysate, and polyalcohol, the action toimprove the withstanding voltage property of the electrolyte capacitorcan be increased, and therefore, such inclusion is preferable.

The concentration of the binder is preferably 0.05-20 mass %, and morepreferably, 0.5-5 mass % in the high boiling point organic solvent witha boiling point of 150° C. or more, or in the conductive auxiliaryliquid.

The examples of the epoxy compound or its hydrolysate can includepolyethylene glycol diglycidyl ether, diethylene glycol glycidyl,glycidyl methacrylate, epoxypropanol (i.e., glycidol), methyl glycidylether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidylether, epoxybutane (i.e., glycidyl methane), epoxypentane glycidylethane), epoxyhexane glycidyl propane), epoxyheptane (i.e., glycidylbutane), epoxyoetane (i.e., glycidyl pentane), epoxycyclohexane,ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,butylene glycol diglycidyl ether, pentylene glycol diglycidyl ether,hexylene glycol diglycidyl ether, and glycerol diglycidyl ether. Theexamples of the silane compound or its hydrolysate can include3-glycidoxypropyitrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane,p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane,3-isocyanatepropyltriethoxysilane, tetramethoxysilane,tetraethoxysilane, and silica sol. The examples of the polyalcohol caninclude polyethylene glycol, polypropylene glycol, and polybutyleneglycol.

EXAMPLES

Next, the present invention is explained more in detail with referenceto the Examples, but the construction of the present invention shouldnot be limited to the Examples alone. It is noted that in the Examples,the indication of % for the concentration or content is mass unlessotherwise noted.

The Examples are described here for an electrolyte capacitor produced byusing a conductive polymer as an electrolyte, which is prepared by usingthe oxidant dopant agent for conductive polymer production and itssolution.

[Preparation of Oxidant Dopant Agent Solution For Conductive PolymerPreparation (1)]

Regarding the preparation (1) of the oxidant dopant agent for conductivepolymer preparation solution (which can be hereinafter simplifies as“oxidant dopant agent solution”), the oxidant dopant agent solution ofExamples 1 to 30 and the oxidant dopant agent solution of ComparativeExample 1 are shown. The oxidant dopant agent solutions of Examples 1 to30 were used in the production of the tantalum electrolyte capacitors ofExamples 31 to 60, and the oxidant dopant agent solution of ComparativeExample 1 was used in the production of the tantalum electrolytecapacitor of Comparative. Example 2, as described later.

Example 1

5.7 kg of ferric naphthalenesulfonate (a molar ratio of 1:2.70 for ironversus naphthalenesulfonic acid) was dissolved to prepare 10 kg of anethanol solution (1% of water content).

Then, 10 kg of the ethanol solution of the ferric naphthalenesulfonateabove was put into a reaction vessel having an internal volume of 20 L,into which 300 g of dibutyl phosphate (5.26% with respect to the ferricnaphthalenesulfonate) was added. Then, there was heated such that thetemperature of the contents reached 80° C., and a reflux was continuedfor one hour to prepare an oxidant dopant agent solution.

Example 2

Except that replacing with 10 kg of the ethanol solution in which 5.7 kgof ferric naphthalenesulfonate was dissolved, 10 kg of an ethanolsolution (1% of water content) in which 4.7 kg of ferricnaphthalenesulfonate (a molar ratio of 1:2.70 for iron versusnaphthalenesulfonic acid) and 1 kg of ferric methanesulfonate (a molarratio of 1:2.70 for iron versus methane sulfonic acid) was used. Otherthan the above, the same procedure as Example 1 was carried out toprepare an oxidant dopant agent solution.

In Example 2, 300 g of dibutyl phosphate was contained in the oxidantdopant agent solution in the same manner as Example 1. The quantity ofthe dibutyl phosphate was 5.26% with respect to the organic ferricsulfonate made by ferric naphthalenesulfonate and ferricmethanesulfonate.

Example 3

Except that replacing with 10 kg of the ethanol in which 5.7 kg offerric naphtalenesulfonate was dissolved, 10 kg of an ethanol solution(1% of water content) in which 4.7 kg of ferric p-toluenesulfonate (amolar ratio of 1:2.70 for iron versus p-toluenesulfonic acid) and 1 kgof ferric methaesulfonate (a molar ratio of 1:2.70 for iron versusmethane sulfonic acid) was used. Other than the above, procedure asExample 1 was carried out to prepare an oxidant dopant agent solution.

In Example 3, 300 g of dibutyl phosphate was contained in the oxidantdopant agent solution in the same manner as Example 1. The quantity ofthe dibutyl phosphate was 5.26% with respect to he organic ferricsulfonate made by ferric p-toluenesulfonate and ferric methanesulfonate.

Example 4

Except that replacing with 10 kg of the ethanol solution in which 5.7 kgof ferric naphthalenesulfonate was dissolved, 10 kg of an ethanolsolution (1% of water content) in which 4.7 kg of ferricnaphthalenesulfonate (a molar ratio of 1:2.70 for iron versusnaphthalenesulfonic acid) and 1 kg of ferric p-toluenesulfonate (a molarratio of 1:2.70 for iron versus p-toluenesulfonic acid) was used. Otherthan the above, the same procedure as Example 1 was carried out toprepare an oxidant agent solution.

In Example 4, 300 g of dibutyl phosphate was contained in the oxidantdopant agent solution in the same manner as Example 1. The quantity ofthe dibutyl phosphate was 5.26% with respect to the organic ferricsulfonate made by ferric naphthalenesulfonate and ferricp-toluenesulfonate.

Example 5

Except for replacing 300 g of dibutyl phosphate with 300 g of tributylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 5, the quantity of thetributyl phosphate in the oxidant dopant agent solution was 5.26% withrespect to the ferric naphthalenesulfonate.

Example 6

Except for replacing 300 g of dibutyl phosphate with 500 g of dibutylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 6, the quantity of the dibutylphosphate in the oxidant dopant agent solution was 8.77% with respect tothe ferric naphthalenesulfonate.

Example 7

Except for replacing 300 g of dibutyl phosphate with 100 g of dibutylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 7, the quantity of the dibutylphosphate in the oxidant dopant agent solution was 1.75% with respect tothe ferric naphthalenesulfonate.

Example 8

Except fur replacing 300 g of dibutyl phosphate with 200 g of phosphoricacid, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 8, the quantity of thephosphoric acid in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 9

Except for replacing 300 g of dibutyl phosphate with 200 g ofphosphorous acid, the same procedure as Example 1 was carried out toprepare an oxidant dopant agent solution. In Example 9, the quantity ofthe phosphorous acid in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 10

Except for replacing 300 g of dibutyl phosphate with 300 g of dibutylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 10, the quantity of thedibutyl phosphite in the oxidant dopant agent solution was 5.26% withrespect to the ferric naphthalenesulfonate.

Example 11

Except for replacing 300 g of dibutyl phosphate with 300 g of tributylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 11, the quantity of thetributyl phosphite in the oxidant dopant agent solution was 5.26% withrespect to the ferric naphthalenesulfonate.

Example 12

Except for replacing 300 g of dibutyl phosphate with 200 g of boricacid, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 12, the quantity of the boricacid in the oxidant dopant agent solution was 3.51% with respect to theferric naphthalenesulfonate.

Example 13

Except for replacing 300 g of dibutyl phosphate with 200 g of tributylborate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 13, the quantity of thetributyl borate in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 14

Except for replacing 300 g of dibutyl phosphate with 300 g ofdiethylhexyl phosphate, the same procedure as Example 1 was carried outto prepare an oxidant dopant agent solution. In Example 14, the quantityof the diethylhexyl phosphate in the oxidant dopant agent solution was5.26% with respect to the ferric naphthalenesulfonate.

Example 15

Except for replacing 300 g of dibutyl phosphate with 200 g ofdithiophosphoric acid, the same procedure as Example 1 was carried outto prepare n oxidant dopant agent solution. In Example 15, the quantityof the dithiophosphoric acid in the oxidant dopant agent solution was3.51% with respect to the ferric naphthalenesulfonate.

Example 16

Except for replacing 300 g of dibutyl phosphate with 200 g ofdiethylhexyl dithiophosphate, the same procedure as Example 1 wascarried out to prepare an oxidant dopant agent solution. In Example 16,the quantity of the diethylhexyl dithiophosphate in the oxidant dopantagent solution was 3.51% with respect to the ferricnaphthalenesulfonate.

Example 17

Except for replacing 300 g of dibutyl phosphate with 200 g ofthiophosphoric acid, the same procedure as Example 1 was carried out toprepare an oxidant dopant agent solution. In Example 17, the quantity ofthe thiophosphoric acid in the oxidant dopant agent solution was 3.51%with respect to the ferric naphthalenesulfonate.

Example 18

Except for replacing 300 g of dibutyl phosphate with 300 g of diethylthiophosphate, the same procedure as Example 1 was carried out toprepare an oxidant dopant agent solution. In Example 18, the quantity ofthe diethyl thiophosphate in the oxidant dopant agent solution was 5.26%with respect to the ferric naphthalenesulfonate.

Example 19

Except for replacing 300 g of dibutyl phosphate with 200 g of dimethylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 19, the quantity of thedimethyl phosphate in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 20

Except for replacing 300 g of dibutyl phosphate with 200 g of diethylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 20, the quantity of thediethyl phosphate in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 21

Except for replacing 300 g of dibutyl phosphate with 250 g of dipropylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 21, the quantity of thedipropyl phosphate in the oxidant dopant agent solution was 4.39% withrespect to the ferric naphthalenesulfonate.

Example 22

Except for replacing 300 g of dibutylphosphate with 570 g of dibenzylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 22, the quantity of thedibenzyl phosphate in the oxidant dopant agent solution was 10.00% withrespect to the ferric naphthalenesuifonate.

Example 23

Except for replacing 300 g of dibutyl phosphate with 250 g of diphenylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 23, the quantity of thediphenyl phosphate in the oxidant dopant agent solution was 4.39% withrespect to the ferric naphthaienesulfonate.

Example 24

Except for replacing 300 g of dibutyl phosphate with 200 g of dimethylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 24, the quantity of thedimethyl phosphite in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 25

Except for replacing 300 g of dibutyl phosphate with 200 g of diethylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 25, the quantity of thediethyl phosphite in the oxidant dopant agent solution was 3.51% withrespect to the ferric naphthalenesulfonate.

Example 26

Except for replacing 300 g of dibutyl phosphate with 250 g of dipropylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 26, the quantity of thedipropyl phosphite in the oxidant dopant agent solution was 4.39% withrespect to the ferric naphthalenesulfonate.

Example 27

Except for replacing 300 g of dibutyl phosphate with 350 g of dibenzylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 27, the quantity of thedibenzyl phosphite in the oxidant dopant agent solution was 6.14% withrespect to the ferric naphthalenesulfonate.

Example 28

Except for replacing 300 g of dibutyl phosphate with 300 g of diphenylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 28, the quantity of thediphenyl phosphite in the oxidant dopant agent solution was 5.26% withrespect to the ferric naphthalenesulfonate.

Example 29

Except for replacing 300 g of dibutyl phosphate with 250 g of ethylphosphate, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 29, the quantity of the ethylphosphate in the oxidant dopant agent solution was 4.39% with respect tothe ferric naphthalenesulfonate.

Example 30

Except for replacing 300 g of dibutyl phosphate with 250 g of ethylphosphite, the same procedure as Example 1 was carried out to prepare anoxidant dopant agent solution. In Example 30, the quantity of the ethylphosphite in the oxidant dopant agent solution was 4.39% with respect tothe ferric naphthalenesulfonate.

Comparative Example 1

Without adding 300 g of dibutyl phosphate, the same procedure as Example1 was carried out to prepare an oxidant dopant agent solution.

In order to evaluate the characteristics of the oxidant dopant agentsolutions of Examples 1 to 30 and Comparative Example 1 as preparedabove, conductive polymers were prepared by using them, and therebyobtained conductive polymers were used as electrolyte to producetantalum electrolyte capacitors of Examples 31 to 60 and ComparativeExample 2, and then, the properties thereof were measured.

[Evaluation of Tantalum Electrolyte Capacitor (1)] Example 31

The capacitor element for the tantalum electrolyte capacitor to be usedwas a tantalum sintered body. It was designed to have a rated voltage of16V, an ESR of 20 mΩ or less, a capacitance of 150 μF or more, and aleak current of 100 μA or less.

The capacitor element above was immersed in a monomer solution obtainedby adding 80 ml of ethanol into 20 ml of a mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6. After one minute, it was pulled up and dried at roomtemperature for 10 minutes. Then, the capacitor element above wasimmersed in an oxidant dopant agent dilution solution obtained bydiluting 500 g of the oxidant dopant agent solution of Example 1 with500 g of ethanol. After 30 seconds, it was pulled up and left at roomtemperature for 80 minutes to cause a polymerization to form aconductive polymer layer. Then, thereby obtained capacitor elementhaving formed the conductive polymer layer was immersed in pure water.After 30 minutes, it was pulled out to dry it at 105° C. for 30 minutes.The sequential procedure above was repeated ten times. Then, thecapacitor element above was immersed in the oxidant dopant agentsolution of Example 1. After 30 seconds, it was pulled out and dried at50° C. for 10 minutes. Then, it was immersed in a mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6. One minute later, it was pulled out and left at roomtemperature for 80 minutes to cause polymerization to form a conductivepolymer layer. Then, the capacitor element having formed the conductivepolymer layer was immersed in pure water. After 30 minutes, it waspulled out and dried at 150° C. for 30 minutes. The sequential procedureabove was repeated three times. Then, the electrolyte layer made of theconductive polymer was covered by carbon paste and silver paste. Then,its outside was surrounded by an exterior material to obtain a tantalumelectrolyte capacitor of the Example 1.

Examples 32 to 60 and Comparative Example 2

Except for replacing the oxidant dopant agent solution of Example 1 witheach of the oxidant dopant agent solutions of Examples 2 to 30 andComparative Example 1, the same procedure as Example 31 was carried cutby using each oxidant dopant agent solution, thereby obtaining each oftantalum electrolyte capacitors of Examples 32 to 60 and ComparativeExample 2.

With respect to the tantalum type electrolyte capacitors of Examples 31to 60 and Comparative Example 2 as produced above, the ESR and thecapacitance were measured, as well as the leakage current was measured.The results are shown in Tables 1 and 2, along with the kinds of theoxidant dopant agent solution used. The explanations below are themeasuring methods of the ESR, the capacitance and the leakage current.

ESR:

-   Using an LCR meter (4284A) made by HEWLETT PACKARD Corporation, it    was measured at 100 kHz at a condition of 25° C.

Capacitance:

-   Using an LCR meter (4284A) made by HEWLETT PACKARD Corporation, it    was measured at 120 Hz at a condition of 25° C.

Leakage Current:

-   A voltage of 16V was applied to the capacitor at 25° C. for 60    seconds. Then, a leakage current was measured with a digital    oscilloscope.

In the measurement, ten samples of each Example was used. The values ofESR, as shown in Tables 1 and 2, were obtained by averaging the resultsof the ten samples while rounding off the number of the second decimalplace. The values of capacitance and leakage current, as shown in Tables1 and 2, were obtained by averaging the results of the ten samples whilerounding off the numbers after the decimal point. Also, the kind of theoxidant dopant agent solution used in each of Examples 31 to 60 isexpressed by the number of the Example.

TABLE 1 Oxidant dopant Capacitance Leak current agent solution ESR (mΩ)(μF) (μA) Example 31 Example 1 15.3 160 18 Example 32 Example 2 15.0 16422 Example 33 Example 3 15.5 166 25 Example 34 Example 4 15.2 162 21Example 35 Example 5 15.6 158 29 Example 36 Example 6 15.5 162 17Example 37 Example 7 15.4 157 24 Example 38 Example 8 15.0 156 29Example 39 Example 9 15.1 157 30 Example 40 Example 10 15.3 159 19Example 41 Example 11 15.5 158 27 Example 42 Example 12 15.6 156 25Example 43 Example 13 15.5 156 27 Example 44 Example 14 15.4 160 19Example 45 Example 15 15.4 158 24 Example 46 Example 16 15.5 160 18Example 47 Example 17 15.2 157 22 Example 48 Example 18 15.4 159 19Example 49 Example 19 15.1 160 25 Example 50 Example 20 15.2 160 22

TABLE 2 Oxidant dopant Capacitance Leak current agent solution ESR (mΩ)(μF) (μA) Example 51 Example 21 15.3 159 20 Example 52 Example 22 15.5158 15 Example 53 Example 23 15.5 158 14 Example 54 Example 24 15.2 16127 Example 55 Example 25 15.3 159 23 Example 56 Example 26 15.3 160 21Example 57 Example 27 15.6 157 17 Example 58 Example 28 15.6 156 17Example 59 Example 29 15.3 161 25 Example 60 Example 30 15.3 161 23Comp. Ex. 2 Comp. Ex. 1 15.8 155 1032

As shown in Tables 1 and 2, the tantalum type electrolyte capacitors ofExamples 31 to 60 (which hereinafter can be simply referred to as“capacitor”) had an ESR of 15.0 to 15. 6 mΩ, thereby satisfying the setvalue of the ESR to be 20 mΩ or less; a capacitance of 156 to 166 μF,thereby satisfying the set value of the capacitance to be 150 μF ormore; and a leak current of 14 to 30 μA, thereby satisfying the setvalue of the leak current to be 100 μA or less. In addition, comparedwith the capacitor of Comparative Example 2 shown in Table 2, it wasfound that the leak current was significantly low. In addition, thecapacitors of Examples 31 to 60 were superior to the capacitor ofComparative Example 2 with respect to the ESR and the capacitance.Without causing the characteristic drops in the ESR and the capacitance,they could accomplish a significant reduction of the leak current incomparison with the capacitor of Comparative Example 2.

[Preparation of Oxidant Dopant Agent Solution For Conductive PolymerPreparation (2)]

Regarding the preparation (2) of the oxidant dopant agent for conductivepolymer preparation solution (which can be hereinafter simplifies as“oxidant dopant agent solution”), the oxidant dopant agent solution ofExamples 61 to 91 and the oxidant dopant agent solution of ComparativeExamples 3 and 4 are shown. These oxidant dopant agent solutions wereused in the production of winding-type aluminum electrolyte capacitorsof Examples 92 to 122 and Comparative Examples 5 and 6, as describedlater.

Example 61

5.7 kg of ferric naphthalenesulfonate (a molar ratio of 1:2.70 for ironversus naphthalenesulfonic acid) was dissolved to prepare 10 kg of anethanol solution (1% of water content).

Then, 10 kg of the ethanol solution of the ferric naphthalenesulfonateabove was put into a reaction vessel having an internal volume of 20 L,into which 300 g of dibutyl phosphate and 1 kg of glycerin diglycidylether were added. Then, there was heated such that the temperature ofthe contents reached 80° C., and a reflux was continued for one hour toprepare an oxidant dopant agent solution.

In Example 61, the quantity of the dibutyl phosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate, and the quantity of the glycerin diglycidyl etherwas 17.54% with respect to the ferric naphthalenesulfonate.

Example 62

Except that replacing with 10 kg of the ethanol solution in which 5.7 kgof ferric naphtlalenesulfonate was dissolved, 10 kg of an ethanolsolution (1% of water content) in which 4.7 kg of ferricnaphthalenesulfonate (a molar ratio of 1:2.70 for iron versusnaphthalenesulfonic acid) and 1 kg of ferric methanesulfonate (a molarratio of 1:2.70 for iron versus methane sulfonic acid) was used. Otherthan the above, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 62, 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether were contained in the oxidant dopant agent solution inthe same manner as Example 61. The quantity of the dibutyl phosphate was5.26% with respect to the organic ferric sulfonate constituted by ferricnaphthalenesulfonate and ferric methanesulfonate, and the quantity ofthe glycerin diglycidyl ether was 17.54% with respect to the organicferric sulfonate constituted by ferric naphthalenesulfonate and ferricmethanesulfonate.

Example 63

Except that replacing with 10 kg of the ethanol solution in which 5.7 kgof ferric naphthalenesulfonate was dissolved, 10 kg of an ethanolsolution (1% of water content) in which 4.7 kg of ferricp-toluenesulfonate (a molar ratio of 1:2.70 for iron versusp-toluenesulfonic acid) and 1 kg of ferric methanesulfonate (a molarratio of 1:2.70 for iron versus methane sulfonic acid) was used. Otherthan the above, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 63, 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether were contained in the oxidant dopant agent solution inthe same manner as Example 61. The quantity of the dibutyl phosphate was5.26% with respect to the organic ferric sulfonate constituted by ferricp-toluenesulfonate and ferric methanesulfonate, and the quantity of theglycerin diglycidyl ether was 17.54% with respect to the organic ferricsulfonate constituted by ferric p-toluenesulfonate and ferricmethanesulfonate

Example 64

Except that replacing with 10 kg, of the ethanol solution in which 5.7kg of ferric naphthalenesulfonate was dissolved, 10kg of an ethanolsolution (1% of water content) in which 4.7 kg of ferricnaphthalenesulfonate (a molar ratio of 1:2.70 for iron versusnaphthalenesulfonic acid) and 1 kg of ferric p-toluenesulfonate (a molarratio of 1:2.70 for iron versus p-toluenesulfonic acid) was used. Otherthan the above, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 64, 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether were contained in the oxidant dopant agent solution inthe same manner as Example 61. The quantity of the dibutyl phosphate was5.26% with respect to the organic ferric sulfonate constituted by ferricnaphthalenesulfonate and ferric p-toluenesulfonate, and the quantity ofthe glycerin diglycidyl ether was 17.34% with respect to the organicferric sulfonate constituted by ferric naphthalenesulfonate and ferricp-toluenesulfonate.

Example 65

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 300 g of diethylhexyl phosphate and 1 kg of cresylglycidyl ether, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 65, the quantity of the diethylhexyl phosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate, and the quantity of the cresyl glycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 66

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 300 g of diethylhexyl phosphate and 1 kg ofglycidyl methacrylate, the same procedure as Example 61 was carried outto prepare an oxidant dopant agent solution.

In Example 66, the quantity of the diethylhexyl phosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate, and the quantity of the glycidyl methacrylate was17.54% with respect to the ferric naphthalenesuifonate.

Example 67

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 300 g of diethylhexyl phosphate, 500 g of glycidylmethacrylate and 500 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,the same procedure as Example 61 was carried out to prepare an oxidantdopant agent solution.

In Example 67, the quantity of the diethylhexyl phosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate; and the quantity of the glycidyl methacrylate was8.77% with respect to the ferric naphthalenesulfonate; and the quantityof the 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 8.77% withrespect to the ferric naphthalenesulfonate.

Example 68

Except for replacing 300 g of dibutyl phosphate with 500 g of dibutylphosphate, the same procedure as Example 61 was carried out to preparean oxidant dopant agent solution.

In Example 68, the quantity of the dibutyl phosphate in the oxidantdopant agent solution was 8.77% with respect to the ferricnaphthalenesulfonate. Also, in Example 68, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 69

Except for replacing 300 g of dibutyl phosphate with 100 g of dibutylphosphate, the same procedure as Example 61 was carried out to preparean oxidant dopant agent solution.

In Example 69, the quantity of the dibutyl phosphate in the oxidantdopant agent solution was 1.75% with respect to the ferricnaphthalenesulfonate. Also, in Example 69, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 70

Except fur replacing 300 g of dibutyl phosphate with 200 g of phosphoricacid, the same procedure as Example 61 was carried out to prepare anoxidant dopant agent solution.

In Example 70, the quantity of the phosphoric acid in the oxidant dopantagent solution was 3.51% with respect to the ferricnaphthalenesulfonate. Also, in Example 70, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 71

Except for replacing 300 g of dibutyl phosphate with 200 g ofphosphorous acid, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 71, the quantity of the phosphorous acid in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate. Also, in Example 71, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 72

Except for replacing 300 g of dibutyl phosphate with 300 g of dibutylphosphite, the same procedure as Example 61 was carried out to preparean oxidant dopant agent solution.

In Example 72, the quantity of the dibutyl phosphite in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate. Also, in Example 72, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 73

Except for replacing 300 g of dibutyl phosphate with 300 g of tributylphosphite, the same procedure as Example 61 was carried out to preparean oxidant dopant agent solution.

In Example 73, the quantity of the tributyl phosphite in the oxidantdopant agent solution was 5.26% with respect to the ferric.naphthalenesulfonate. Also, in Example 73, 1 kg of glycerin diglycidylether was contained in the oxidant dopant agent solution in the samemanner as Example 61. The quantity of the glycerin diglycidyl ether was17.54% with respect to the ferric naphthalenesulfonate.

Example 74

Except for replacing 300 g of dibutyl phosphate with 200 g of boricacid, the same procedure as Example 61 was carried out to prepare anoxidant dopant agent solution.

In Example 74, the quantity of the boric acid in the oxidant dopantagent solution was 3.51% with respect to the ferric naphthaleesulfonate. Also, in Example 74, 1 kg of glycerin diglycidyl ether wascontained in the oxidant dopant agent solution in the same manner asExample 61. The quantity of the glycerin diglycidyl ether was 17.54%with respect to the ferric naphthalenesulfonate.

Example 75

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl other with 300 g of tributyl phosphate and 1 kg of glycidylmethacrylate, the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 75, the quantity of the tributyl phosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate, and the quantity of the glycidyl methacrylate17.54% with respect to the ferric naphthalenesulfonate.

Example 76

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of dithiophosphoric acid and 1 kg of2-(3,4-epoxycyclohexyl)ethylmethoxysilane, the same procedure as Example61 was carried out to prepare a oxidant dopant agent solution.

In Example 76, the quantity of the dithiophosphoric acid in the oxidantagent solution was 3.51% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 77

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of diethylhexyl dithiophosphate and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 77, the quantity of the diethylhexyl dithiophosphate in theoxidant dopant agent solution was 3.61% with respect to the ferricnaphthalenesulfonate and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 78

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of thiophosphoric acid and 1 kg of 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure as Example 61was carried out to prepare an oxidant dopant agent solution.

In Example 78, the quantity of the thiophosphoric acid in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 79

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 300 g of diethyl thiophosphate and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 79, the quantity of the diethyl thiophosphate in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 1.54% with respect tothe ferric naphthalenesulfonate.

Example 80

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of dimethyl phosphate and 1 kg of3-glycidoxypropyltrimethoxysine, the same procedure as Example 61 wascarried out to prepare an oxidant dopant agent solution.

In Example 80, the quantity of the dimethyl phosphate in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate, and the quantity of the 3-glycidoxypropyltrimethoxysilane was 17.64% with respect to the ferricnaphthalenesulfonate.

Example 81

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of diethyl phosphate and 1 kg of epoxypolysiloxane X-41-1053 (product name) manufactured by Shin-etsuChemistry Co., Ltd., the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 81, the quantity of the diethyl phosphate in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate; and the quantity of the epoxy polysiloxane“X-41-1053” (product name) was 17.54% with respect to the ferricnaphthalenesulfonate.

Example 82

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 260 g of dipropyl phosphate and 1 kg of epoxypolysiloxane “X-41-1056” (product name) manufactured by Shin-etsuChemistry Co., Ltd., the same procedure as Example 61 was carried out toprepare an oxidant dopant agent solution.

In Example 82, the quantity of the dipropyl phosphate in the oxidantdopant agent solution was 4.39% with respect to the ferricnaphthalenesulfonate; and the quantity of the epoxy polysiloxane““X-41-1056” (product name) was 17.54% with respect to the ferricnaphthalenesulfonate.

Example 83

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 570 g of dibenzyl phosphate and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 83, the quantity of the dibenzyl phosphate in the oxidantdopant agent solution was 10.00% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 84

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 250 g of diphenyl phosphate and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 84, the quantity of the diphenyl phosphate in the oxidantdopant agent solution was 4.39% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 1.54% with respect tothe ferric naphthalenesulfonate.

Example 85

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of dimethyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 85, the quantity of the dimethyl phosphite in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 86

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 200 g of diethyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 86, the quantity of the diethyl phosphite in the oxidantdopant agent solution was 3.51% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 87

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 250 g of dipropyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 87, the quantity of the dipropyl phosphite in the oxidantdopant agent solution was 4.39% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 88

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 350 g of dibenzyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 88, the quantity of the dibenzyl phosphite in the oxidantdopant agent solution was 6.14% with respect to the ferricnaphthaleuesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 89

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 300 g of diphenyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 89, the quantity of the diphenyl phosphite in the oxidantdopant agent solution was 5.26% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 90

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 250 g of ethyl phosphate and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 90, the quantity of the ethyl phosphate in the oxidant dopantagent solution was 4.39% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Example 91

Except for replacing 300 g of dibutyl phosphate and 1 kg of glycerindiglycidyl ether with 250 g of ethyl phosphite and 1 kg of2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the same procedure asExample 61 was carried out to prepare an oxidant dopant agent solution.

In Example 91, the quantity of the ethyl phosphite in the oxidant dopantagent solution was 4.39% with respect to the ferricnaphthalenesulfonate; and the quantity of the2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 17.54% with respect tothe ferric naphthalenesulfonate.

Comparative Example 3

There was prepared 10 kg of an ethanol solution (1% of water content)including ferric naphthalenesulfonate (a molar ratio of 1:2.70 for ironversus naphthalenesulfonic acid) at a concentration of 57%, which wasused as an oxidant dopant agent solution as Comparative Example 3. Theoxidant dopant agent solution of Comparative Example 3 was used toproduce a winding-type aluminum electrolyte capacitor, and itscomposition was the same as the oxidant dopant agent solution ofComparative Example 1. When the oxidant dopant agent solution of Example61 is compared with the oxidant dopant agent solution of ComparativeExample 3, the oxidant dopant agent solution of Comparative Example 3did not include dibutyl phosphate nor glycerin diglycidyl ether.

Comparative Example 4

Without adding 300 g of dibutyl phosphate, the same procedure as Example61 was carried out to prepare an oxidant dopant agent solution. InComparative Example 4, the oxidant dopant agent solution contained17.54% of glycerin diglycidyl ether with respect to the ferricnaphthalenesulfonate in the same manner as the oxidant dopant agentsolution of Example 61, but it did not contain dibutyl phosphate.

In order to evaluate the characteristics of the oxidant &pant agentsolutions of Examples 61 to 91 and Comparative Examples 3 and 4 asprepared above, conductive polymers were prepared by using them, andthereby obtained conductive polymers were used as electrolyte to producewinding-type aluminum electrolyte capacitors of Examples 92 to 122 andComparative Examples 5 and 6, and then, the properties thereof weremeasured.

[Evaluation of Winding-Type Aluminum Electrolyte Capacitor (1)] Example92

In Example 92, a conductive polymer was prepared by using the oxidantdopant agent solution of Example 61, and then, a winding-type aluminumelectrolyte capacitor was prepared by using the conductive polymer as anelectrolyte.

A surface of an aluminum foil was applied to an etching treatment. Then,the aluminum foil after the etching treatment was immersed in a 12%ammonium aqueous solution. Then, the aluminum foil in the ammoniumaqueous solution was applied to a voltage of 75V to form a dielectriclayer made of an oxide film of aluminum on the surface of the aluminumfoil to serve as a positive electrode. A lead terminal was attached tothe positive electrode. Also, a lead terminal was attached to a negativeelectrode made of an aluminum foil. These positive electrode at dnegative electrode having lead terminals were wound with an interventionof a separator to manufacture a capacitor element. The capacitor elementmanufactured here was a winding-type aluminum electrolyte capacitorhaving a set value of the ESR to be 30 mΩ or less, a set value of thecapacitance to be 50 μF or more, a setting value of the leak current tobe 100 μA or less, and a set value of the breakdown voltage to be 50V ormore.

The capacitor element above was immersed in as monomer solution obtainedby adding 80 ml of ethanol into 20 ml of a mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6. After one minute, it was pulled up and dried at 50°C, for 10 minutes. Then, the capacitor element above was immersed in 100ml of the oxidant dopant agent solution of Example 61 for 16 seconds.After pulling it up, it was heated at 70° C. for two hours and then at180° C. for one hour to polymerize the monomers, thereby forming anelectrolyte layer of as conductive polymer having a polymer backbone ofa copolymer of 3,4-ethylenedioxythiophene and butylatedethylenedioxythiophene. Then, the outer surface was surrounded by anexterior material to obtain a winding-type aluminum electrolytecapacitor of Example 92.

Examples 93 to 122 and Comparative Examples 5 and 6

Except for replacing the oxidant dopant agent solution of Example 61with each of the oxidant dopant agent solutions of Examples 62 to 91 andComparative Examples 3 and 4, the same procedure as Example 92 wascarried out by using each oxidant dopant agent solution, therebyobtaining each of winding-type aluminum electrolyte capacitors ofExamples 93 to 122 and Comparative Examples 5 and 6.

Regarding the winding-type aluminum electrolyte capacitors of Examples92 to 122 and Comparative Examples 5 and 6 (hereinafter, which can besimply called as “capacitor”), the ESR, the capacitance, the leakagecurrent and the breakdown voltage were measured. The results are shownin Tables 3 and 4. In addition, the methods for measurements of the ESR,the capacitance and the leak current were the same as described before.The manner shown in Tables 3 and 4 are the same as described in Table 1,except for the ESR shown by rounding off to an integer. The breakdownvoltage was measured by using PRk650-2.5 manufactured by MatsusadaPrecision Inc. at a condition of 25° C. while raising the voltage at aspeed of 1 V/m. Each example was measured for ten samples, and the valueof the breakdown voltage shown in Tables 3 and 4 is an average of theten samples while rounding off to an integer.

TABLE 3 Oxidant Leak Breakdown dopant agent ESR Capacitance currentvoltage solution (mΩ) (μF) (μA) (V) Example 92 Example 61 19 53 5 72Example 93 Example 62 17 54 12 70 Example 94 Example 63 19 55 20 69Example 95 Example 64 18 54 12 71 Example 96 Example 65 19 53 5 71Example 97 Example 66 17 54 6 72 Example 98 Example 67 17 55 6 72Example 99 Example 68 19 54 5 71 Example 100 Example 69 18 52 16 69Example 101 Example 70 19 55 21 69 Example 102 Example 71 19 54 20 69Example 103 Example 72 19 55 7 71 Example 104 Example 73 19 54 21 69Example 105 Example 74 19 52 21 69 Example 106 Example 75 19 53 19 69Example 107 Example 76 20 54 18 70 Example 108 Example 77 19 53 5 70Example 109 Example 78 20 55 20 71 Example 110 Example 79 19 53 7 70Example 111 Example 80 17 55 6 72 Example 112 Example 81 18 54 4 72

TABLE 4 Oxidant Leak Breakdown dopant agent ESR Capacitance currentvoltage solution (mΩ) (μF) (μA) (V) Example 113 Example 82 18 53 4 72Example 114 Example 83 20 52 4 71 Example 115 Example 84 20 52 3 72Example 116 Example 85 17 55 8 70 Example 117 Example 86 18 54 7 70Example 118 Example 87 19 53 5 71 Example 119 Example 88 20 52 4 71Example 120 Example 89 20 52 4 72 Example 121 Example 90 17 54 17 69Example 122 Example 91 17 54 16 69 Comp. Ex. 5 Comp. Ex. 3 20 52 970 35Comp. Ex. 6 Comp. Ex. 4 22 49 450 65

As shown in Tables 3 and 4, the capacitor of Examples 92 to 122 had: anESR of 17 to 20mΩ thereby satisfying the set value of the ESR to be 30mΩ or less; a capacitance of 52 to 55 μF, thereby satisfying the setvalue of the capacitance to be 50 μF or more: a leak current of 3 to 21μA, thereby satisfying the set clue of the leak current to be 100 μA orless; and a breakdown voltage of 69 to 72V, thereby satisfying the setvalue of the breakdown voltage of 50V or more. In addition, thesecapacitors had a lower leak current than the capacitors of ComparativeExamples 5 and 6 as shown in Table 4.

Also, the capacitor of this Examples of 92 to 122 had an ESR equivalentto, or lower than, the capacitors of Comparative Examples 5 and 6, and acapacitance equivalent to, or higher than, the capacitors of ComparativeExamples 5 and 6. Therefore, without bringing about a characteristicdrop in the ESR and the capacitance, the leak current can besignificantly reduced in comparison with the capacitors of ComparativeExamples 5 and 6.

Also, regarding the breakdown voltage, the capacitors of Examples 92 to122 were high. Even in the winding-type aluminum electrolyte capacitorsthat are demanded to satisfy the requirement to be superior in thewithstanding voltage property, it was found that such a requirementcould be met in the winding-type aluminum electrolyte capacitorsprepared by using an electrolyte of the conductive polymer when it wasprepared by using the oxidant dopant agent of the present invention.

[Evaluation of the Winding-Type Aluminum Electrolyte Capacitor (2)]

In this evaluation (2) of the winding-type aluminum electrolytecapacitors, the capacitor characteristics of winding-type aluminumelectrolyte capacitors of Examples 123 to 125 were evaluated, which weredifferent in the monomers from the winding-type aluminum electrolytecapacitors of the evaluation (1).

Example 123

Except for replacing the monomer mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6 with butylated ethylenedioxythiophene alone as amonomer, the same procedure as Example 92 was carried out to produce awinding-type aluminum electrolytic capacitor as Example 123.

Example 124

Except for replacing the monomer mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6 with butylated ethylenedioxythiophene alone as amonomer, the same procedure as Example 97 was carried out to produce awinding-type aluminum electrolytic capacitor as Example 124.

Example 125

Except for replacing the monomer mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6 with butylated ethylenedioxythiophene alone as amonomer, the same procedure as Example 98 was carried out to produce awinding-type aluminum electrolytic capacitor as Example 125.

Comparative Example 7

Except for replacing the oxidant dopant agent solution of Example 61with the oxidant dopant agent solutions of Comparative Example 3, thesame procedure as Example 123 was carried out to prepare a winding-typealuminum electrolyte capacitor of Comparative Example 7.

Comparative Example 8

Except for replacing the oxidant dopant agent solution of Example 61with the oxidant dopant agent solutions of Comparative Example 4, thesame procedure as Example 123 was carried out to prepare a winding-typealuminum electrolyte capacitor of Comparative Example 8.

Regarding the winding-type aluminum electrolyte capacitors of Examples123 to 126 and Comparative Examples 7 and 8 (hereinafter, which can besimply called as “capacitor”), the ESR, the capacitance, the leakagecurrent and the breakdown voltage were measured. The results are shownin Table 5. In addition, the methods for measuring the ESR, thecapacitance, the leak current and the breakdown voltage were the same asdescribed before. The manner shown in Table 5 is the same as describedin Table 3.

TABLE 5 Oxidant Leak Breakdown dopant agent ESR Capacitance currentvoltage solution (mΩ) (μF) (μA) (V) Example 123 Example 61 20 52 1 72Example 124 Example 66 20 52 1 74 Example 125 Example 67 20 52 1 74Comp. Ex. 7 Comp. Ex. 3 22 51 521 41 Comp. Ex. 8 Comp. Ex. 4 24 48 42367

As shown in Table 5, the capacitors of Examples 123 to 125 each had anESR of 20 mΩ, thereby satisfying the set value of the ESR to be 30 mΩ orless; a capacitance of 52 μF, thereby satisfying the set value of thecapacitance to be 50 μF or more; a leak current of 1 μA, therebysatisfying the set value of the leak current to be 100 μA or less; and abreakdown voltage of 72 to 74V, thereby satisfying the set value of thebreakdown voltage of 50V or more. In addition, these capacitors had alower leak current than the capacitors of Comparative Examples 7 and 8.

Also, the capacitors of Examples of 123 to 125 had an ESR slightly lowerthan the capacitors of Comparative Examples 7 and 8, and a capacitanceslightly higher than the capacitors of Comparative Examples 7 and 8.Therefore, without bringing about a characteristic drop in the ESR andthe capacitance, the leak current can be significantly reduced incomparison with the capacitors of Comparative Examples 7 and 8.

Also, regarding the breakdown voltage, the capacitors of Examples 123 to125 were high. Even in the winding-type aluminum electrolyte capacitorsthat are demanded to satisfy the requirement to be superior in thewithstanding voltage property, it was found that such a requirementcould be met.

Furthermore, following comparisons are made between the Examples inwhich the same oxidant dopant agent solution was use. The capacitor ofExample 123 had less leak current than the capacitor of Example 92, bothusing the oxidant dopant agent solution of Example 61 in the samemanner. The capacitor of Example 124 had less leak current than thecapacitor of Example 97, both using the oxidant dopant agent solution ofExample 66 in he same manner. The capacitor of Example 125 had less leakcurrent than the capacitor of Example 98, bath using the oxidant dopantagent solution of Example 67 in the same manner. In other words, thecapacitors of Example 123, Example 124 and Example 125 used onlybutylated ethylenedioxythiophene as a monomer, whereas the capacitor ofExample 92, Example 97 and Example 98 used the mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6 as a monomer, and the formers had a leak current lowerthan the latters.

[Evaluation of Tantalum Electrolyte Capacitor (2)]

In Examples 31 to 60 described before, the oxidant dopant agentsolutions of Examples 1 to 30 of the present invention were used tocarry out so-called the “on-site polymerization” to form conductivepolymer layers on a capacitor element, which were used, as electrolyteto produce the tantalum electrolyte capacitors. Their characteristicevaluations were shown as the evaluation (1) of the tantalum electrolytecapacitor. By contrast, in the evaluation (2) of the tantalumelectrolyte capacitor, a first electrolyte layer of a conductive polymerlayer was formed on a capacitor element by means of so-called “on-sitepolymerization” by using the oxidant dopant agent solution of Example 1of the present invention; and then, on the first electrolyte layer, asecond electrolyte layer, or a second and a third electrolyte layers,i.e., conductive polymer layer(s) formed by using a π conjugated systemconductive polymer dispersion liquid, thereby producing a tantalumelectrolyte capacitor, and evaluating the characteristics thereof.

Then, prior to describing the Examples, Production Examples of πconjugated system conductive polymer dispersion liquid [I] and [II],which were used in the Examples, are described first.

Preparation Example of Conductive Polymer Dispersion Liquid (1)

1 L of pure water was added into a separable flask with a stirrer with ainternal volume of 2 L, into which 170 g of sodium styrenesulfonate and30 g of hydroxyethylacrylate were added. Then, 1 g of ammoniumpersulfate as an oxidant added into the solution. There, apolymerization reaction of styrenesulfonic acid and hydroxyethylacrylate was carried out for 12 hours. The reaction liquid after thepolymerization treated with an ultrafiltration device [VIVAFLOW 200(product name) made by Sartorius Corporation, at a condition of amolecular weight fraction of 50,000] to remove free components havinglow molecular weights in the liquid. Then, water was added there toadjust the concentration into 3%.

With respect to the copolymer of styrenesulfonic acid and hydroxyethylacrylate as obtained above, the weight average molecular weight wasestimated by using a gel filtration column. As a result, it wasestimated as 180,000 based on dextran as a calibration standard.

600 g of a 3% aqueous solution of the copolymer of styrenesulfonic acidand hydroxyethyl acrylate was put in a stainless steel container with aninternal volume of 1 L, into which 0.3 g of ferrous sulfate having 7hydrates was added. Then, 4 mL 3,4-ethylenedioxythiophene was graduallydropped there.

They were stirred with a stirrer blade made of stainless steel, and apositive electrode was attached to the container, and a negativeelectrode was attached to the base of the stirrer blade. A constantcurrent of 1 mA/cm2 was applied to carry out an electrolytic oxidationpolymerization for 18 hours.

After the electrolytic oxidation polymerization above, the mixture wasdiluted with 6 times of water. Then, a dispersion treatment was carriedout by using an ultrasonic homogenizer [Nippon Seiki Co. Ltd., US-T300(product name)] for two hours. Then, 100 g of cation exchange resin[AMBERLITE 120B (product name)] manufactured by Organo Corporation wasadded, and the mixture was stirred for one hour. Then, the mixture wasfiltered with a filter paper No. 131 manufactured by Toyo Roshi Kaisha,Ltd. The treatments by the cation exchange resin followed by thefiltration were repeated three times to remove all the cationiccomponents, such as iron ions, in the liquid.

Thereby treated liquid was filtered with a filter having a pore size of1 μm. The filtered liquid was treated with an ultrafiltration device[VIVAFLOW 200 (product name) made by Sartorius Corporation, at acondition of a molecular weight fraction of 50,000], to remove freecomponents having low molecular weights the liquid. The liquid astreated above was diluted with water to adjust its concentration of thesolution at 2%. Then, into 50 g of the solution, 3 g of dimethylsulfoxide was added to obtain a conductive polymer dispersion liquid(I).

Preparation Example of Conductive Polymer Dispersion Liquid (II)

200 g of 3% sulfonated polyester [PLASGOAT Z-561 (product name)manufactured by Goo Chemical Co., Ltd.; weight average molecular weightof 27,000] aqueous solution put into a beaker with an internal volume of1 L. 2 g of ammonium persulfate was added there and dissolved bystirring with a stirrer. Then, 0.4 g of 40% aqueous solution of ferricsulfate was added. While stirring 3,4-ethylenedioxythiophene (3 mL) wasdropped slowly there to polymerize the 3,4-ethylenedioxythiophene for 24hours.

After the polymerization above, the mixture was diluted with 4 times ofwater in volume. Then, a dispersion treatment was carried out by usingan ultrasonic homogenizer [Nippon Seiki Co., Ltd., US-T300 (productname)] for 30 minutes. Then, 100 g of cation exchange resin [AMBERLITE120B (Product name)] manufactured by Organo Corporation was added, andthe mixture was stirred for one hour. After stirring with a stirrer forone hour, filtration was performed by using a filter paper, No. 131 madeby Toyo Roshi Kaisha, Ltd. The operations from the dispersion to thefiltration described above were repeated three times to remove all thecationic components.

The filtered liquid above was passed through a filter having a pore sizeof 1 μm. Thereby filtered liquid was treated with an ultrafiltrationdevice [VIVAFLOW 200 (product name) made by Sartorius Corporation, at acondition of a molecular weight fraction of 50,000] to remove freecomponents having low molecular weights. The solution above was dilutedwith water to adjust its concentration at 5%. Then, into 40 g of thesolution, 4 g of dimethyl sulfoxide were added to obtain a conductivepolymer dispersion liquid (II).

Example 126

For the capacitor element of the tantalum electrolyte capacitor ofExample 126, a tantalum sintered body having been designed to have arated voltage of 16V an ESR of 20 mΩ or less, a capacitance of 150 μF ormore, and a leak current of 100 μA or less was used.

The capacitor element above was immersed in a monomer solution obtainedby adding 80 ml of ethanol into 20 ml of a mixture, solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6. After one minute, it was pulled up and dried at roomtemperature for 10 minutes. Then, the capacitor element above wasimmersed in an oxidant dopant agent dilution solution obtained by mixing500 g of the oxidant dopant agent solution of Example 1 with 500 g ofethanol. After 30 seconds, it was pulled up and left at room temperaturefor 80 minutes to cause a polymerization to form a conductive polymerlayer. Then, the capacitor element having formed the conductive polymerlayer was immersed in pure water. After 30 minutes, it was pulled outand dried at 70° C. for 30 minutes. The operation above was repeatedfour times to form a first electrolyte layer made of a conductivepolymer on the capacitor element through the “on-site polymerization” ofthe monomer mixture of 3,4-ethylenedioxythiophene and butylatedethylenedioxythiophene at a mass ratio 4:6. In the oxidant dopant agentsolution of Example 1 used in the production of the conductive polymerconstituting the first electrolyte layer, 5.26% of dibutyl phosphate wascontained with respect to the ferric naphthalenesulfonate, as explainedbefore.

Then, the capacitor element having formed the first electrolyte layermentioned above was immersed in the conductive polymer dispersion liquid(II). After one minute, it was pulled up and dried at 150° C., for 30minutes. The operation above was repeated three times to form a secondelectrolyte layer on the first electrolyte layer made by the “on-sitepolymerization” as mentioned above. The second electrolyte layer was alayer formed by impregnation and dry of the conductive polymerdispersion liquid (II).

Then, the electrolyte layer was covered by carbon paste and silverpaste. Then, its outside was surrounded by an exterior material toobtain a tantalum electrolyte capacitor of the Example 126.

Example 127

The same capacitor element as Example 126 was used. In the same manneras Example 126, the same dilution solution of the oxidant dopant agentsolution as Example 1 was used. Then, the monomer mixture of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6 was polymerized to form a first electrolyte layer madeof a conductive polymer on the capacitor element.

Then, the capacitor element above was immersed in the conductive polymerdispersion liquid (I) for 2 minutes, and then it was pulled up, and thenit was dried at 150° C. for 30 minutes. The operation above was repeatedtwice to form a second electrolyte layer on the first electrolyte layermade by the “on-site polymerization” as mentioned above. The secondelectrolyte layer was a layer formed by impregnation and dry of theconductive polymer dispersion liquid (I) (which is hereinafter referredto as “second electrolyte layer made of the conductive polymerdispersion liquid (I)”).

Furthermore, the capacitor element above was immersed in the conductivepolymer dispersion liquid (II) for one minute, and then it was takenout, and then it was dried at 150° C. for 30 minutes. Thereby, on thesecond electrolyte layer made of the conductive polymer dispersionliquid (I), a third electrolyte layer was formed by immersing into theconductive polymer dispersion liquid (II) followed by drying it (whichis hereinafter simply referred to as “third electrolyte layer made ofthe conductive polymer dispersion liquid (II)).”

Then, the electrolyte layer was covered by carbon paste and silver pastethen, its outside was surrounded by an exterior material to obtain atantalum electrolyte capacitor of the Example 127.

With respect to the tantalum electrolyte capacitors of Examples 126 and127 (which can be hereinafter simply called as “capacitor”), the ESR,the capacitance and the leakage current were measured in the same manneras described before. The results are shown in Table 6, along with thekinds of the oxidant dopant agent solution used. In addition, the mannerto show the ESR, the capacitance, the leak current in Table 6 is thesame as described in Table 1.

TABLE 6 Oxidant Leak dopant agent ESR Capacitance current solution (mΩ)(μF) (μA) Example 126 Example 1 14.7 158 9 Example 127 Example 1 14.4156 4

Also, as shown it Table 6, the capacitors of Examples 126 and 127 had anESR of 14.4 to 14.7 mΩ, thereby satisfying the set value of the ESR tobe 20 mΩ or less; a capacitance of 156 to 158 μF, thereby satisfying theset value of the capacitance to be 150 μF or more; and a leak current of4 to 9 μA, thereby satisfying the set value of the leak current to be100 μA or less.

Also, the capacitors of Examples 126 and 127 (tantalum electrolytecapacitor), in the same manner, are compared with the tantalum solidelectrolytic capacitor of Example 31 which used the oxidant dopant agentof the Example 1, The capacitor of Examples 126 and 127 had a leakcurrent lower than the capacitor of Example 31.

That is, the leak current of the capacitor of Example 31 was 18 μA asshown in Table 1, whereas the leak current of the capacitor of Example126 was 9 μA and the leak current of the capacitor of Example 127 was 4μA, as shown in Table 6. Namely, the leak current of the capacitors ofthese Examples 126 and 127 was lower than the leak current of thecapacitor of Example 31. It was found that the leak current could belowered by forming the second electrolyte layer or the second and thirdelectrolyte layers made of the conductive polymer of the π conjugatedsystem conductive polymer dispersion liquid on the first electrolytelayer made of the conductive polymer formed by so-called the “on-sitepolymerization.”

[Evaluation of Winding-Type Aluminum Electrolyte Capacitor (3)]

In the evaluation (3) of the winding-type aluminum solid electrolyticcapacitor, the followings were done. An inorganic acid ester typeadditive such as phosphate or phosphite was mixed with a monomer. Themixture of the monomer and the inorganic acid ester type additive wasmixed with an organic ferric sulfonate solution during the manufacturingprocess of the electrolyte capacitor. In the presence of the monomer, anoxidant dopant agent solution for conductive polymer preparation wasconstituted by including the organic ferric sulfonate, and the inorganicacid ester type additive such as phosphate or the phosphite, so as toform the oxidant dopant agent solution for conductive polymerpreparation of the present invention. By using the oxidant dopantsolution for conductive polymer production, the monomer was polymerizedto form an electrolyte layer made of as conductive polymer.

Example 128

A surface of an aluminum foil was applied to an etching treatment. Then,the aluminum foil after the etching treatment was immersed in a 12%ammonium aqueous solution. Then, the aluminum foil in the ammoniumaqueous solution was applied to a voltage of 75V to form a dielectriclayer made of an oxide film of aluminum on the surface of the aluminumfoil to serve as a positive electrode. A lead terminal was attached tothe positive electrode. Also, a lead terminal was attached to a negativeelectrode made of an aluminum foil. These positive electrode andnegative electrode having lead terminals were wound with an interventionof a separator to manufacture a capacitor element. The capacitor elementprepared here was a winding-type aluminum electrolyte capacitor havingas set value of the ESR to be 30 mΩ or less, a set value of thecapacitance to be 50 μF or more, a setting value of the leak current tobe 100 μA or less, and a set value of the breakdown voltage to be 50V ormore, also having a cavity volume of the element being 0.1 ml.

Then, into 20 ml of a monomer mixture made by mixing3,4-ethylenedioxythiophene with butylated ethylenedioxythiophene at amass ratio 4:6, 4 ml of dibutyl phosphate (4 ml of this dibutylphosphate was to be 4.24 g at a mass) and 76 ml of ethanol were added toprepare a monomer solution.

Also, 5.7 kg of ferric naphthalenesulfonate (a molar ratio of 1:2.70 forthe iron and the naphthalenesulfonic acid) was dissolved to prepare 10kg of an ethanol solution (1% of water content). Then, 10 kg of theethanol solution of the ferric naphthalenesulfonate above was put into areaction vessel having an internal volume of 20 L, into which 1 kg ofglycerin diglycidyl ether was added. The contents were heated to reach atemperature of 80° C. A reflux was continued for one hour to prepare anoxidant dopant agent solution.

This oxidant dopant agent solution contained a quantity of the glycerindiglycidyl ether at 17.54% with respect to the ferricnaphthalenosulfonate. This oxidant dopant agent solution had the sameconstitution as the oxidant dopant agent solution of Example 61 exceptfor excluding dibutyl phosphate.

Also, when producing the winding-type electrolyte capacitor, first thecapacitor element was immersed in 100 ml of the monomer solution asprepared above. After 60 seconds, it was pulled up and dried at 50° C.for ten minutes. During the drying, the ethanol could almost dry, sothat 24% of the volumes in the capacitor element were satisfied with themonomer and the dibutyl phosphate. In particular, 4% thereof could beoccupied by the dibutyl phosphate.

Then, the capacitor element above was immersed in 100 ml of the oxidantdopant agent solution (110 g by mass) which did not include the dibutylphosphate as prepared. After 20 seconds, it was pulled out. By theoperation above, 76% of the volumes inside the capacitor element werefilled with the oxidant dopant agent solution. Here, the oxidant dopantagent solution filled inside the capacitor element was 0.076 ml. Sinceit has a specific gravity is 1.1, the mass of the oxidant dopant agentsolution filled inside of the capacitor element was 0.0836 g. From thecomposition ratio of each of the ingredients in the oxidant dopantagent, the mass of the ferric naphthalenesulfonate was obtained. As aresult, the mass of the ferric naphthalenesulfonate filled inside thecapacitor element was 0.0433 g. By contrast, the mixture of the monomerand the dibutyl phosphate, which was filled inside the capacitorelement, was 0.024 ml. The dibutyl phosphate 0.024 ml of the mixture ofthe monomer and the dibutyl phosphate was 0.004 ml. Since the mass ofthe dibutyl phosphate was 0.00424 g as shown above. In Example 128, therelation between the ferric naphthalenesulfonate and the dibutylphosphate, which were filled inside the capacitor element, wasequivalent to the case in which 9.79% by mass of dibutyl phosphate wasadded with respect to the ferric naphthalenesulfonate.

Then, it was heated at 70° C. for two hours and then at 180° C. for onehour to polymerize the monomers, thereby forming an electrolyte layer ofa conductive polymer having a polymer backbone of a copolymer of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene. Then,the outer surface was surrounded by an exterior material to obtain awinding-type aluminum electrolyte capacitor of Example 128.

Example 129

3.9 kg of ferric naphthalenesulfonate molar ratio of 1:2.70 for ironversus naphthalenesulfonic acid) was dissolved to prepare 9.32 kg of anethanol solution (1% of water content).

Then, 0.68 kg of glycerin diglycidyl ether was added into the ethanolsolution of the ferric naphthalenesulfonate above. Then, there washeated such that the temperature of the contents reached 80° C. and areflux was continued for one hour to prepare an oxidant dopant agentsolution.

Then, into 20 ml of a monomer mixture made by mixing3,4-ethylenedioxythiophene with butylated ethylenedioxythiophene at amass ratio 4:6, 4 ml of diethylhexyl phosphate (this was equivalent to3.86 g by mass of the diethylhexyl phosphate) and 45 ml of ethanol wereadded to prepare a monomer solution.

Then, the same capacitor element as Example 128 was immersed in 100 mlof the oxidant dopant agent solution as prepared above for 30 seconds.After it was pulled out, it was dried at 105° C. for 30 minutes. Duringthe drying, the ethanol could almost dry, so that approximately 31% ofthe volume inside the capacitor element was filled with the mixture offerric naphthalenesulfonate and glycerin diglycidyl ether that werederived from the oxidant dopant agent solution. Since the mixture offerric naphthalenesulfonate and glycerin diglycidyl ether had a specificgravity of approximately 1.48, the mass of the mixture of the ferricnaphthalenesulfonate and glycerin diglycidyl ether, filled inside thecapacitor element, was approximately 0.046 g. From the composition ratioof each ingredient in the mixture of the ferric naphthalenesulfonate andthe glycerin diglycidyl ether, it was found that the ferricnaphthalenesulfonate filled inside the capacitor element wasapproximately 0.039 g. Then, the capacitor element above was immersed in69 ml of the monomer solution including the diethylhexyl phosphate whichhad prepared as explained before. After 10 seconds, it was pulled out.By the operation above, 69% of the volumes inside the capacitor elementwere filled with the monomer solution. The monomer solution filledinside the capacitor element in this way was 0.069 ml. From the quantityof the addition of the diethylhexyl phosphate at the time of thepreparation of the monomer solution, the volume of the diethylhexylphosphate occupied in the monomer solution was 0.004 ml. The mass of thediethylhexyl phosphate was 0.00386 g, that to be clear from the above.Therefore, in Example 129, the relation between the ferricnaphthalenesulfonate and the diethylhexyl phosphate, which were filledinside the capacitor element, was equivalent to the case in which 9.90%by mass of diethylhexyl phosphate was added with respect to the ferricnaphthalenesulfonate.

Then, it was heated at 70° C. for two hours and then at 180° C. for onehour to polymerize the monomers, thereby forming an electrolyte layer ofa conductive polymer having a polymer backbone of a copolymer of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene. Then,the outer surface was surrounded by an exterior material to obtain awinding-type aluminum electrolyte capacitor of Example 129.

Example 130

Into 20 ml of a monomer mixture made by mixing3,4-ethylenedioxythiophene with butylated ethylenedioxythiophene at amass ratio 4:6, 4 ml of diphenyl phosphate (this was equivalent to 3.04g by mass of diphenyl phosphate) was added to prepare a monomersolution.

24 ml of the monomer solution above was mixed with 76 ml of the oxidantdopant agent solution (83. 6 g by mass) same as used in Example 128. Thesame capacitor element as used in Example 128 was immersed in 100 ml ofthe mixture solution obtained. After 30 seconds, it was pulled out. Bythe operation above, 0.076 ml of the oxidant dopant agent solution and0.024 ml of the monomer solution were filled inside the capacitorelement. The mass of 0.076 ml of the oxidant dopant agent solution was0.0836, that was clear from the above. From the composition ratio ofeach ingredient of the oxidant dopant agent solution, it was found thatthe mass of the ferric naphthalenesulfonate filled inside the capacitorelement was 0.0433 g. By contrast, 0.024 ml of the monomer solutioncontained 0.004 ml of diphenyl phosphate. The mass of 0.004 ml of thediphenyl phosphate was 0.00304 g as described above. Therefore, inExample 130, the relation between the ferric naphthalenesulfonate andthe diphenyl phosphate, which were filled inside the capacitor element,was equivalent to the case in which 7.02% by mass of diphenyl phosphatewas added with respect to the ferric naphthalenesulfonate.

Then, it was heated at 70° C. for two hours and then at 180° C. for onehour to polymerise the monomers, thereby forming an electrolyte layer ofa conductive polymer having a polymer backbone of a copolymer of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene. Then,the outer surface was surrounded by an exterior material to obtain awinding-type aluminum electrolyte capacitor of Example 130.

Example 131

Except for replacing dibutyl phosphate with dibutyl phosphite, the sameprocedure as Example 128 was carried out to prepare a winding-typealuminum electrolyte capacitor of Example 131.

Example 132

Except for replacing diethylhexyl phosphate with diethylhexyl phosphite,the same procedure as Example 129 was carried out to prepare awinding-type aluminum electrolyte capacitor of Example 139.

Example 133

Except for replacing diphenyl phosphate with diphenyl phosphite, thesame procedure as Example 130 was carried out to prepare a winding-typealuminum electrolyte capacitor of Example 133.

Regarding the winding-type aluminum electrolyte capacitors of Examples128 to 133 (hereinafter, which can be simply called as “capacitor”), theESR, the capacitance, the leakage current and the breakdown voltage weremeasured. The results are shown in Table 7. In addition, the methods formeasuring the ESR, the capacitance, the leak current and the breakdownvoltage were the same as described before. The manner shown in Table 7is the same as described in Table 3.

TABLE 7 Capacitance Leak current Breakdown ESR (mΩ) (μF) (μA) voltage(V) Example 128 20 55 9 69 Example 129 19 52 5 71 Example 130 17 54 6 72Example 131 20 54 10 69 Example 132 19 52 6 72 Example 133 18 54 5 72

As shown in Table 7, the capacitors of Examples 128 to 133 had an ESR of17 to 20 mΩ, thereby satisfying the set value of the ESR to be 30 mΩ orless; a capacitance of 52 to 55 μF, thereby satisfying the set value ofthe capacitance to be 50 μF or more; a leak current of 5 to 10 μA,thereby satisfying the set value of the leak current to be 100 μA orless; and a breakdown voltage of 69 to 72V, thereby satisfying the setvalue of the breakdown voltage of 50V or more. Also, the capacitors ofExamples 128 to 133 had a lower leak current and a higher breakdownvoltage than the capacitors of Comparative Examples 5 and 6 as shown inTable 4.

[Evaluation of Winding-Type Aluminum Electrolyte Capacitor (4)]

In this evaluation (4) of the winding-type aluminum electrolytecapacitor, a conductive polymer prepared by using the oxidant dopantagent solution for conductive polymer preparation of the presentinvention was used along with a conductive auxiliary liquid, therebypreparing a winding-type aluminum electrolyte capacitor. Then, itscharacteristics were evaluated.

First, a preparation example of the conductive auxiliary liquid isexplained before explaining the production of the winding-type aluminumelectrolyte capacitor.

Preparation Example of Conductive Auxiliary Liquid (1)

Into 500 g of γ-butyrolactone put in an 1L beaker with a stirrer, 50 gof hydroxybenzene carboxylic acid, 5 g of nitrobenzoic acid (i.e.,nitrobenzene carboxylic acid) and 1 g of3-glycidoxypropyltrimethoxysilane were added. Ethylamine was furtheradded to adjust the pH at 4. After stirring was continued for 24 hours,a conductive auxiliary liquid (1) was obtained.

The conductivity of this conductive auxiliary liquid (1) was measuredunder a condition of 25° C. by using a conductivity measurementinstrument (F-55) manufactured by Horiba, Ltd. The conductivity of thisconductive auxiliary liquid was 0.9 mS/cm.

Preparation Example of Conductive Auxiliary Liquid (2)

Into 500 g of ethylene glycol put in an 1L beaker with a stirrer, 50 gof phthalic acid, 5 g of nitrophenol and 5 g of polyethylene glycoldiglycidyl ether were added. Ethylamine was further added to adjust thepH at 6. After stirring was continued for 24 hours, a conductiveauxiliary liquid (2) was obtained.

The conductivity of this conductive auxiliary liquid (2) was measuredunder a condition of 25° C. by using a conductivity measurementinstrument (F-55) manufactured by Horiba, Ltd. The conductivity of thisconductive auxiliary liquid (2) was 0.5 mS/cm.

Preparation Example of Conductive Auxiliary Liquid (3)

Into 500 g of ethylene glycol put in an 1L beaker with a stirrer. 50 gof phthalic acid, 5 g of nitrobenzoic acid, 100 g of tributyl phosphate,2 g of polyethylene glycol 400, and 5 g of polysiloxane were added.Diethylamine was further added therein to adjust the pH at 3. Afterstirring was continued for 24 hours, a conductive auxiliary liquid (3)was obtained.

The conductivity of this conductive auxiliary liquid (3) was measuredunder a condition of 25° C. by using a conductivity measurementinstrument (F-55) manufactured by Horiba, Ltd. The conductivity of thisconductive auxiliary liquid (3) was 0.6 mS/cm.

Example 134

A surface of an aluminum foil was applied to an etching treatment. Then,the aluminum foil after the etching treatment was immersed in a 12%ammonium aqueous solution. Then, the aluminum foil in the ammoniumaqueous solution was applied to a voltage of 130V to form a dielectriclayer made of an oxide film of aluminum on the surface of the aluminumfoil to serve as a positive electrode. A lead terminal was attached tothe positive electrode. Also, a lead terminal was attached to a negativeelectrode made of an aluminum foil. These positive electrode andnegative electrode having lead terminals were wound with an interventionof a separator to manufacture a capacitor element. The capacitor elementprepared here was a winding-type aluminum electrolyte capacitor having aset value of the ESR to be 30 mΩ or less, a set value of the capacitanceto be 30 μF or more, a setting value of the leak current to be 100 μA orless, and a set value of the breakdown voltage to be 65V or more.

The capacitor element above was immersed in a monomer solution obtainedby adding 70 ml of ethanol into 30 ml of as mixture solution of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene at amass ratio of 4:6. Then, it was pulled up and dried at 50° C. for 10minutes. Then, the capacitor element above was immersed in 100 ml of theoxidant dopant agent solution of Example 61. After pulling it up, it washeated at 50° C. for 30 hours and then at 180° C. for one hour topolymerize the monomers, thereby forming an electrolyte layer of aconductive polymer having a polymer backbone of a copolymer of3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene. Then,the capacitor element above was immersed in the conductive auxiliaryliquid (1), followed by pulling it out. Then, the outer surface wassurrounded by an exterior material to obtain a winding-type aluminumelectrolyte capacitor of Example 134.

Example 135

The conductive auxiliary liquid (1) was replaced with the conductiveauxiliary liquid prepared (2). Other than the replacement above, thesame procedure as Example 134 was carried out to produce winding-typealuminum electrolyte capacitor of Example 135.

Example 136

The conductive auxiliary liquid (1) was replaced with the conductiveauxiliary liquid prepared (3). Other than the replacement above, thesame procedure as Example 134 was carried out to produce winding-typealuminum electrolyte capacitor of Example 136.

Example 137

Except for replacing the oxidant dopant agent solution of Example 61with the oxidant dopant agent solutions of Example 66, the sameprocedure as Example 134 was carried out to prepare a winding-typealuminum electrolyte capacitor of Example 137.

Example 138

The conductive auxiliary liquid (1) was replaced with the conductiveauxiliary liquid prepared (2). Other than the replacement above, thesame procedure as Example 137 was carried out to produce a winding-typealuminum electrolyte capacitor of Example 138.

Example 139

The conductive auxiliary liquid (1) was replaced with the conductiveauxiliary liquid prepared (3). Other than the replacement above, thesame procedure as Example 137 was carried out to produce winding-typealuminum electrolyte capacitor of Example 139.

Comparative Example 9

100 ml of the oxidant dopant agent solution of Example 61 was replacedwith 100 ml of the oxidant dopant agent solution of Comparative Example3. In addition, the process of immersing in the conductive auxiliaryliquid (1) was not carried out. Other than the changes noted here, thesame procedure as Example 134 was carried out to produce a winding-typealuminum electrolyte capacitor of Comparative Example 9.

Comparative Example 10

100 ml of the oxidant dopant agent solution of Example 61 was replacedwith 100 ml of the oxidant dopant agent solution of Comparative Example4. In addition, the process of immersing in the conductive auxiliaryliquid (1) was not carried out. Other than the changes noted here, thesame procedure as Example 134 was carried out to produce a winding-typealuminum electrolyte capacitor of Comparative Example 10.

Regarding the winding-type aluminum electrolyte capacitors of Examples134 to 139 and Comparative Examples 9 and 10 (hereinafter, which can besimply called as “capacitor”), the ESR, the capacitance, the leakagecurrent and the breakdown voltage were measured, in the same manner asdescribed before. The results are shown in Table 8 in the same manner asTable 3.

TABLE 8 Breakdown Capacitance Leak voltage ESR (mΩ) (μF) current (μA)(V) Example 134 22 34 2 103 Example 135 21 34 2 100 Example 136 21 35 1102 Example 137 23 34 1 104 Example 138 22 35 1 103 Example 139 22 34 1104 Comp. Ex. 9 23 27 1092 42 Comp. Ex. 10 27 32 880 55

As shown in Table 8, the capacitors of Examples 134 to 139 each had: anESR of 21 to 23 mΩ, thereby satisfying the set value of the ESR to be 30mΩ or less; a capacitance of 34 to 35 μF, thereby satisfying the setvalue of the capacitance to be 30 μF or more; a leak current of 1 to 2μA, thereby satisfying the set value of the leak current to be 100 μA orless; and a breakdown voltage of 100 to 104V, thereby satisfying the setvalue of the breakdown voltage of 65V or more. In addition, thesecapacitors had a lower leak current than the capacitors of ComparativeExamples 9 and 10.

INDUSTRIAL UTILITY

According to the present invention, there can be provided an oxidantdopant agent for conductive polymer production, and a solution thereof,in which they are capable of producing a conductive polymer suitable inproducing an electrolyte capacitor having a low leak current. Inaddition, there can be provided a conductive polymer prepared by usingeither of them, in which the conductive polymer is suitable in producingan electrolyte capacitor having a low leak current. Also, there can beprovided an electrolyte capacitor using the conductive polymer as anelectrolyte, in which the electrolyte capacitor has a low leak current.

1. An oxidant dopant agent for preparing a conductive polymer,comprising: an organic ferric sulfonate; and at least one kind selectedfrom the group consisting of phosphoric acid, phosphate, phosphorousacid, phosphite, boric acid, borate, thiophosphoric acid, thiophosphate,dithiophosphoric acid and dithiophosphate.
 2. The oxidant dopant agentfor preparing the conductive polymer according to claim 1, furthercomprising a glycidyl group containing compound or its ring-openingcompound.
 3. The oxidant dopant agent for preparing the conductivepolymer according to claim 1, wherein the organic ferric sulfonate has amolar ratio of iron to an organic sulfonic acid, wherein the molar ratiois lower than 1:3 in view of the organic sulfonic acid.
 4. The oxidantdopant agent for preparing the conductive polymer according to claim 1,wherein said at least one kind selected from the group consisting of thephosphoric acid, the phosphate, the phosphorous acid, the phosphite, theboric acid, the borate, the thiophosphoric acid, the thiophosphate, thedithiophosphoric acid and the dithiophosphate is contained at an amountof 1 to 100% by mass standard with respect to the organic ferricsulfonate.
 5. A solution of an oxidant dopant agent for preparing aconductive polymer, wherein 20 to 70 mass % of the oxidant dopant agentfor preparing the conductive polymer according to claim 1 is dissolvedin water, an alcohol or a mixture of the water and the alcohol.
 6. Aconductive polymer, wherein using the oxidant dopant agent for preparingthe conductive polymer according to claim 1, wherein at least one kindof a monomer selected from the group consisting of a thiophene or itsderivative, a pyrrole or its derivative, and an aniline or itsderivative is subject to an oxidation polymerization to prepare aconductive polymer.
 7. A conductive polymer, wherein using the solutionof the oxidant dopant agent for preparing the conductive polymeraccording to claim 5, wherein at least one kind of a monomer selectedfrom the group consisting of a thiophene or its derivative, a pyrrole orits derivative, and an aniline or its derivative is subject to anoxidation polymerization to prepare a conductive polymer.
 8. Theconductive polymer according to claim 6, wherein the monomer is thederivative of the thiophene, wherein the derivative of the thiophene is3,4-ethylenedioxythiophene or an alkylated ethylenedioxythiophenerepresented by a general formula (7),

(in the formula, R⁴ represents hydrogen or an alkyl group having acarbon number of 1 to 10).
 9. The conductive polymer according to claim8, wherein the derivative of the thiophene is a mixture of3,4-ethylenedioxythiophene and the alkylated ethylenedioxythiophene. 10.An electrolyte capacitor, comprising: the conductive polymer accordingto claim 6 used as an electrolyte.
 11. An electrolyte capacitorcomprising an electrolyte, the electrolyte comprising: the conductivepolymer according to claim 6, and another conductive polymer obtainedfrom a dispersion liquid of a π conjugated system conductive polymerincluding a polymer anion as a dopant.
 12. The electrolyte capacitoraccording to claim 10, further comprising a conductive auxiliary liquid,wherein the conductive auxiliary liquid comprises: a high boiling pointorganic solvent having a boiling point of 150° C. or more; or a highboiling point organic solvent having a boiling point of 150° C. or more,and an aromatic compound having at least one hydroxyl group or carboxylgroup.